CN101512799B - Current collector, electrode, and non-aqueous electrolyte secondary battery - Google Patents

Current collector, electrode, and non-aqueous electrolyte secondary battery Download PDF

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Publication number
CN101512799B
CN101512799B CN2007800323307A CN200780032330A CN101512799B CN 101512799 B CN101512799 B CN 101512799B CN 2007800323307 A CN2007800323307 A CN 2007800323307A CN 200780032330 A CN200780032330 A CN 200780032330A CN 101512799 B CN101512799 B CN 101512799B
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China
Prior art keywords
protuberance
collector body
active material
electrode
base material
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CN101512799A (en
Inventor
住原正则
伊藤修二
古结康隆
柏木克巨
桐原信幸
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

Provided is an electrode capable of effectively spreading or mitigating a stress generated by expansion and contraction of an active material. An active material layer is formed on a particular current collector so as to prepare an electrode. The current collector includes a base and a plurality of protrusions formed to extend outside from the surface of the base. A cross section of the respective protrusions in the thickness direction of the current collector has a tapered shape having a width in the direction parallel to the base surface narrowed toward the direction in which the protrusions extend from the base surface.

Description

Collector body, electrode and rechargeable nonaqueous electrolytic battery
Technical field
The present invention relates to collector body, electrode and rechargeable nonaqueous electrolytic battery.
Background technology
Recently, the miniaturization and the lightweight of electronic equipment and communication apparatus constantly develop, and the demand of secondary cell that becomes the power supply of these equipment increases.Lithium secondary battery particularly because have high power capacity and high-energy-density, charge is also good, so its occupation rate of market is very big.Representative lithium secondary battery mainly can embed with the negative pole of the carbon materials of removal lithium embedded and contains LiCoO by containing 2Deng transition metal and the positive pole of the composite oxides of lithium constitute.But, be accompanied by the multifunction of present electronic equipment and communication apparatus, also require the further raising of further high-energy-densityization and charge for lithium secondary battery.
For such requirement, gazed at by forming the alloy system active material that alloy embeds lithium with lithium.As the alloy system active material, for example known alloy that silicon, tin, germanium is arranged and contain these elements, oxide, nitride etc.The alloy system active material has high power capacity.For example, the theoretical discharge capacity of silicon is approximately 4199mAh/g, is equivalent to about 11 times (for example, with reference to patent documentations 1) of the theoretical discharge capacity of graphite.But the existing problem that should solve of alloy system active material is: when embedding the charging of lithium ion, structure greatly changes and expands.In the active material layer that contains the alloy system active material (hereinafter referred to as " alloy system active material layer "), under the effect of the stress that produces in the expansion that is accompanied by the alloy system active material, the unfavorable conditions such as distortion of the cracking, alloy system active material layer that the alloy system active material particle takes place easily peeling off from the collector body, collector body and even electrode.These unfavorable conditions become the electronic conductivity that reduces between alloy system active material layer and the collector body, the reason that reduces the charge of battery.
In view of the problem of alloy system active material, for example proposed to contain the electrode (for example, with reference to patent documentation 2) of the alloy system active material layer of specific collector body and film like.At this, collector body is made of copper alloy, and hot strength is 400N/mm 2More than, proportional limit is 160N/mm 2More than, modulus of elasticity is 1.1N/mm 2More than, the surface roughness Ra on the formed surface of alloy system active material layer is 0.01～1 μ m.In addition, in patent documentation 2, putting down in writing: for the surface roughness Ra with the collector body surface is adjusted into above-mentioned predetermined scope, adopt galvanoplastic, form the thrust that constitutes by copper on the collector body surface.In addition, also putting down in writing: adopt vacuum vapour deposition, galvanoplastic etc., form the alloy system active material layer of film like on the collector body surface.The technology of patent documentation 2 at the bond strength that improves alloy system active material layer and collector body, prevent that aspect alloy system active material layer the peeling off from the collector body be effective to a certain extent.But, if just improve the bond strength of alloy system active material layer and collector body, then owing to not absorbing the swelling stress of alloy system active material fully, so can on electrode, produce the distortion of fold, be full of cracks etc. inevitably.
For relaxing the swelling stress of alloy system active material, proposed to set up the technology (for example, with reference to patent documentation 3,4) in space in the inside of alloy system active material layer.Patent documentation 3 discloses a kind of electrode, and it is included in that irregular collector body is set up on the surface and at the irregular surface of setting up of collector body formed film like alloy system active material layer.If this electrode is loaded in the battery and carries out initial charging, then under the effect of the swelling stress of alloy system active material, in film like alloy system active material layer, produce the space along the concavo-convex of collector body surface.In the technology of patent documentation 3, the swelling stress of alloy system active material is absorbed by this space.But, in patent documentation 3, owing to be to produce the space by charging, so in film like alloy system active material layer, it is difficult that the space is distributed equably.Therefore, in this film like alloy system active material layer, have that existence because of the space can relax the part of swelling stress and because of not existing the space can not relax the part of swelling stress.For this reason, often can not obtain sufficient stress alleviation effects, thereby electrode is deformed.
Patent documentation 4 discloses a kind of electrode, and it is included in the alloy system active material layer that is made of a plurality of columns that the surface is formed with the collector body of predetermined relief pattern and contains the alloy system active material.Relief pattern forms by photoetch.Column is formed: from the recess of the relief pattern of collector body or protuberance surface to extending perpendicular to this surperficial direction.The scheme that column only forms on the recess or the protuberance surface of predetermined relief pattern has in the advantage of technology of patent documentation 4, also brings deficiency.Advantage is to have the space between adjacent column, makes the swelling stress to side surface direction of column obtain relaxing by this space.Weakness is the interface that the swelling stress to the collector body direction of column concentrates on column and recess or protuberance, thereby column is easily from recess or protuberance sur-face peeling.Therefore, in the technology of patent documentation 4,, prevent fully that column from being that peeling off of alloy system active material layer is difficult though the distortion of electrode is prevented to a certain extent.
In addition, people have also proposed a kind of electrode, it contains collector body and film like alloy system active material layer, and the value of (surface roughness Ra of film like alloy system active material layer)-(surface roughness Ra of collector body) is 0.1 μ m above (for example, with reference to a patent documentation 5).Usually, if employing vacuum vapour deposition etc. form film on the collector body surface, then can obtain having the film of the surface roughness identical with collector body surface cardinal principle.On the other hand, in patent documentation 5, the film that forms with usual way is implemented processing such as sandblast, surface grinding, the surface roughness of film just is adjusted into above-mentioned specific value by this.Thus, the swelling stress of alloy system active material is relaxed.Patent documentation 5 disclosed technology are preventing aspect the alloy system active material cracking it is effectively to a certain extent, but form aspect the film on whole collector body surface, with patent documentation 2 and 3 disclosed technology without any variation.Therefore, film peeling off and the distortion of electrode etc. from the collector body taken place easily.
On the other hand, for improving the bond strength of collector body and active material layer, in the technology that makes collector body surface asperitiesization, above-mentioned patent documentation has in addition also proposed various schemes.For example, can exemplify out the surface that makes particulate high speed impact rolled copper foil by nozzle, thereby form small concavo-convex method on this surface (for example, with reference to patent documentation 6).This method is by the nozzle ejection particulate time, because the generation VELOCITY DISTRIBUTION, so be difficult to be formed uniformly concavo-convex at the long side direction and the short side direction on collector body surface.
In addition, also can exemplify out irradiating laser on metal forming, count the asperities method (for example, with reference to patent documentation 7) of the concavo-convex metal forming of 0.5～10 μ m with 10 mean roughness to form surface roughness.In the technology of patent documentation 7, by irradiating laser with heating of metal paper tinsel partly, thereby make the evaporation of metal of this part and form recess.But,, the high heat that constitutes more than the fusing point of metal of metal forming will be imposed on metal forming by laser radiation.In addition, because laser shines linearly, therefore on metal forming, there are illuminated portion and non-illuminated portion.Therefore, be difficult to prevent from metal forming, to fluctuate, fold, warpage etc.Moreover, when the metal forming below the employed thickness of the collector body of lithium secondary battery is 20 μ m is carried out laser radiation, because the deviation of laser output often occurs in the such unfavorable condition of perforate on the metal forming.
In addition, for improving the bond strength and the electrical conductivity of active material layer and collector body, proposed to have specific concavo-convex collector body (for example, with reference to patent documentation 8).Figure 21 (a)～(e) is the stereogram of formation that schematically illustrates the collector body of patent documentation 8.The collector body of patent documentation 8 is formed with following concavo-convex regularly: when the local part in the surface of metal forming caves in, and highlighting to the outside from another surface in another surface with the corresponding part of above-mentioned local part.Have so concavo-convex collector body when it is made, can produce distortion such as fluctuation, fold, warpage inevitably.
In addition, a kind of electrode has also been proposed, it comprises: by be processed to form irregular perforate degree by embossing is the collector body that constitutes of the punch metal below 20% and the active material layer of filling at the recess of collector body, and the protuberance of collector body exposes or be attached with active material (for example, with reference to patent documentation 9) at protuberance.Figure 22 (a)～(c) is the longitudinal section of formation that schematically illustrates the electrode 101～103 of patent documentation 9.Electrode 101 shown in Figure 22 (a) comprises the active material layer 111 that forms irregular collector body 110 and filled at the recess 110b of collector body 110, also is attached with active material layer 111 on the protuberance 110a surface of collector body 110.At Figure 22 (b) with in the electrode 102,103 (c), expose protuberance 120a, the 130a of collector body 120,130 respectively.In patent documentation 9, owing at the perforate degree being implements embossing processing to form concavo-convexly on the punch metal below 20%, thereby the collector body that obtains does not have sufficient mechanical.Therefore, often cause the unfavorable condition that lead rupture is such.
Patent documentation 1: the spy opens the 2002-83594 communique
Patent documentation 2: the spy opens the 2003-7305 communique
Patent documentation 3: the spy opens the 2001-283834 communique
Patent documentation 4: the spy opens the 2004-127561 communique
Patent documentation 5: the spy opens the 2002-279972 communique
Patent documentation 6: the spy opens the 2002-79466 communique
Patent documentation 7: the spy opens the 2003-258182 communique
Patent documentation 8: the spy opens the 2002-270186 communique
Patent documentation 9: the spy opens the 2005-32642 communique
Summary of the invention
The object of the present invention is to provide a kind of collector body, it is effective at the aspects such as distortion of the cracking that prevents the alloy system active material particle, alloy system active material layer peeling off from the collector body, collector body and even electrode for the electrode of the alloy system active material layer that comprises collector body and form on collector body surface.
Another object of the present invention is to provide a kind of electrode, it comprises collector body of the present invention and alloy system active material layer, it is effectively for the further raising of the high-energy-densityization of battery and charge, even and long-term the use, also keep to high level initial performance.
Another purpose of the present invention is to provide a kind of rechargeable nonaqueous electrolytic battery, and it contains electrode of the present invention, has high-energy-density and good charge.
The present invention relates to a kind of collector body, it comprises base material portion and forms a plurality of protuberances that extend to the outside of base material portion from base material portion surface, wherein, the section of the protuberance of collector body thickness direction towards the direction of protuberance extension, is the coniform shape of the narrowed width of the direction that is parallel to base material portion surface from base material portion surface.
Preferred protuberance has height L, and at the diameter D of the protuberance of 0.3L height 0.3Greater than diameter D at 0.8L protuberance highly 0.8
Preferably at the diameter D of the protuberance of 0.5L height 0.5With diameter D at 0.3L protuberance highly 0.3Ratio (D 0.5/ D 0.3) be below 0.98.
Preferably at the diameter D of the protuberance of 0.8L height 0.8With diameter D at 0.5L protuberance highly 0.5Ratio (D 0.8/ D 0.5) be more than 0.4.
In the section of collector body thickness direction, represent that preferably among the line angulation θ on line and the surface of expression base material portion of side of protuberance at least one is greater than 90 ° but less than 160 °.
Preferably between base material portion and protuberance, there is not the interface, and the crystalline portion that contains from base material portion to the protuberance continued presence at least and have identical substantially crystalline state.
Preferred protuberance forms by compression process not.
Preferably on the bearing of trend of protuberance, the head portion of protuberance is the plane.
In addition, the invention still further relates to a kind of electrode, it comprises collector body of the present invention and active material layer.
Preferred active material layer comprises and contains active material and form the columnar-shaped particle that extends to the outside of collector body from the protuberance surface of collector body.
Columnar-shaped particle preferably tilts with respect to the direction with the collector body Surface Vertical.
Preferred columnar-shaped particle is the duplexer that contains a plurality of column pieces of active material.
Active material is preferably the compound that is selected from least a kind alloy system negative electrode active material among silicon, tin, germanium and the aluminium and/or contains the alloy system negative electrode active material.
The compound that contains the alloy system negative electrode active material preferably is selected from least a kind among at least a kind alloy, oxide and the sulfide that contains the alloy system negative electrode active material.
In addition, the invention still further relates to a kind of rechargeable nonaqueous electrolytic battery, it comprises the nonaqueous electrolyte to electrode and lithium-ion-conducting of electrode of the present invention, this electrode.
Collector body of the present invention has for relaxing or disperseing to be accompanied by the expansion of alloy system active material and contraction and the stress that produces is effective structure.Therefore, in the electrode of the present invention that contains collector body of the present invention and alloy system active material layer, distortion of the cracking, alloy system active material layer that is difficult to take place the alloy system active material particle peeling off from the collector body, collector body and even electrode etc.This effect mainly results from the structure of collector body, so even long-term the use also can reduce hardly.
In addition, the rechargeable nonaqueous electrolytic battery that contains electrode of the present invention has high-energy-density, and charge is good, even long-term the use, the deterioration of its performance is also considerably less.Therefore, the power supply as the various mobile electronic apparatus of multifunction is very useful.
Description of drawings
Fig. 1 is the vertical view that schematically illustrates as the formation of the collector body of one of embodiments of the present invention.
Fig. 2 is the cutaway view of the cutting plane line II-II of collector body shown in Figure 1.
Fig. 3 is the longitudinal section of section configuration of the protuberance of other execution mode of expression.
Fig. 4 represents the formation of the roller that the roller processing method is adopted.Fig. 4 (a) is the stereogram of the outward appearance of expression roller.Fig. 4 (b) is the stereogram that amplifies the surf zone of the roller shown in the presentation graphs 4 (a).
Fig. 5 is the stereogram that schematically illustrates the formation of wanting portion of the collector body manufacturing installation that contains roller shown in Figure 4.
Fig. 6 is the longitudinal section that the plastic deformation that the roller processing method carries out is adopted in explanation.
Fig. 7 is the longitudinal section of the formation of the expression collector body that adopts other execution mode that the roller processing method makes.
Fig. 8 is the longitudinal section of the plastic deformation carried out of employing roller processing method of other execution mode of explanation.
Fig. 9 is the longitudinal section that schematically illustrates the formation of electrode of the present invention.
Figure 10 is the cutaway view of formation that schematically illustrates the electrode of other execution mode.
Figure 11 is the exploded stereogram that schematically illustrates as the formation of the convoluted rechargeable nonaqueous electrolytic battery of one of embodiments of the present invention.
Figure 12 is the cutaway view that schematically illustrates as the formation of the laminate type battery of one of embodiments of the present invention.
Figure 13 schematically illustrates the formation as the collector body of one of embodiments of the present invention.
Figure 14 schematically illustrates the formation as the collector body of one of embodiments of the present invention.
Figure 15 is the longitudinal section that schematically illustrates the formation of evaporation coating device.
Figure 16 is the scanning electron microscope photo of the negative pole section of embodiment 4.
Figure 17 is the scanning electron microscope photo of the negative pole section of embodiment 5.
Figure 18 is the scanning electron microscope photo of the negative pole section of embodiment 6.
Figure 19 is the scanning electron microscope photo of the negative pole section of embodiment 7.
Figure 20 is the scanning electron microscope photo of the negative pole section of comparative example 1.
Figure 21 is the stereogram of formation that schematically illustrates the collector body of prior art.
Figure 22 is the longitudinal section of formation that schematically illustrates the electrode of prior art.
Embodiment
[collector body]
Fig. 1 is the vertical view that schematically illustrates as the formation of the collector body 1 of one of embodiments of the present invention.Fig. 2 is the cutaway view of the cutting plane line II-II of collector body 1 shown in Figure 1.
Collector body 1 comprises base material portion 10 and protuberance 11.
Base material portion 10 forms laminar or film like, and the section configuration of thickness direction roughly is rectangle.In addition, the thickness direction of base material portion 10 is consistent with the thickness direction of collector body 1.In addition, the thickness direction of collector body 1 is with consistent perpendicular to the direction on collector body 1 surface.
Using under the situation of collector body 1 as negative electrode collector, base material portion 10 usefulness constitute with the material that electrochemical reaction can not take place lithium.As the object lesson of this material, for example can enumerate copper, nickel, iron and contain alloy of at least a kind in these elements etc.Among them, copper and copper alloy preferably.Copper and copper alloy is preferred in easily operation, aspect low-cost.As copper alloy, for example can list and contain zinc-copper, stanniferous copper, silver-bearing copper, contain composite alloy more than 2 kinds of precipitation hardening type alloys such as zirconium copper, chromium-copper, tellurium copper, titanium copper, beryllium copper, iron content copper, phosphorous copper, aluminum bronze and these alloys etc.The not special restriction of the content of the dissimilar metal beyond the copper removal of copper alloy, but 0.01 weight % of copper alloy total weight～10 weight % preferably.
Using under the situation of collector body 1 as positive electrode collector, base material portion 10 is used in that anodal current potential zone is not dissolved and constitutes with electrochemical reaction can not take place lithium material.As the instantiation of this material, for example can list aluminium, aluminium alloy, stainless steel, titanium etc.
Base material portion 10 for example uses the material that electrochemical reaction can not take place with lithium, can make according to the manufacture method of common metal forming, metallic film, nonwoven fabrics etc.With the metal forming that adopts the employed copper and copper alloy of negative electrode collector is example, for example can list electrolytic copper foil, cathode copper Alloy Foil, rolled copper foil, copper alloy foil, calendering copper alloy foil and it is implemented the resulting paper tinsel of asperities processing etc.As implementing the resulting paper tinsel of asperities processing, preferably electrolytic copper foil, rolled copper foil, copper alloy foil etc.In addition, positive electrode collector for example can use the metal forming that is made of aluminium, aluminium alloy, stainless steel, titanium etc., nonwoven fabrics etc.Can certainly implement the asperities processing to the employed metal forming of positive electrode collector.Such metal forming, metallic film, nonwoven fabrics etc. can be used as collector body and use with material web in the manufacture method of collector body 1 described later.
The not special restriction of the thickness of base material portion 10, but preferably 5 μ m～100 μ m, more preferably 8～35 μ m.If the thickness deficiency of base material portion 10 5 μ m then often make the mechanical strength of collector body 1 become insufficient, the fracture of the electrode the when reduction of the operability of the collector body 1 when generating electrodes is made easily, battery charge etc.On the other hand,, then can guarantee the mechanical strength of collector body 1, but collector body 1 shared volume in electrode integral body increases, often can not fully realize the high capacity of battery if the thickness of base material portion 10 surpasses 100 μ m.
Protuberance 11 for example has the function of appendix active material layer on its surperficial at least a portion.Protuberance 11 is a plurality of, forms on one or two surface of the thickness direction of base material portion 10.In addition, protuberance 11 is formed from the surface of base material portion 10 and extends to the outside of base material portion 10.
In other words, protuberance 11 forms in mode continuous in base material portion 10.Preferred formation is: between base material portion 10 and protuberance 11, do not have the interface, and at least 1 of crystalline portion with roughly the same crystalline state from base material portion 10 to protuberance 11 continued presences.Thus, the bond strength of base material portion 10 and protuberance 11 is able to further raising, thereby can further prevent protuberance 11 peeling off from the base material portion 10 effectively.
In addition, the surface in base material portion 10, the mode that 2 adjacent protuberances 11 are isolated to have the gap forms.Therefore, in the section of the thickness direction of collector body shown in Figure 21, between 2 adjacent protuberances 11, there is concave surface 12.
Protuberance 11 usefulness form with the material identical materials that constitutes base material portion 10.
The section on the thickness direction of collector body 1 of protuberance 11 (being designated hereinafter simply as " section of protuberance 11 ") has coniform shape.In more detail, the section of protuberance 11 has coniform shape, to the bearing of trend of protuberance 11, its width (being designated hereinafter simply as " section width of protuberance 11 ") that is parallel on the direction on base material portion 10 surfaces slowly or continuously diminishes this coniform shape from the surface of base material portion 10.In the present embodiment, the section of protuberance 11 roughly is the platform shape.In addition, in the present embodiment, protuberance 11 be shaped as the frustum of a cone, if but the section of protuberance 11 has coniform shape, the then not special restriction of the shape of protuberance 11.In addition, in the present embodiment, on the bearing of trend of protuberance 11, the top portion of protuberance 11 becomes the plane that is roughly parallel to base material portion 10 surfaces, but the present invention is not limited thereto.For example, also can be the plane that is not parallel to base material portion 10 surfaces, to have concavo-convex hemisphere planar, dome-shaped etc.If these shapes are effective for the bond strength that improves protuberance 11 and active material layer then.
In addition, in the section of protuberance 11, have at protuberance 11 under the situation of height L, at the diameter D of 0.3L protuberance 11 highly 0.3Be preferably greater than diameter D at the protuberance 11 of 0.8L height 0.8That is D preferably, 0.3＞D 0.8At this, the height of so-called protuberance 11, the length of the vertical line that the top portion (being designated hereinafter simply as " the top portion of protuberance 11 ") that is meant the protuberance 11 from the bearing of trend of protuberance 11 hangs down to the surface of base material portion 10.The top portion of protuberance 11 be plane and this plane parallel under the situation on base material portion 10 surfaces, the arbitrfary point from the plane of the top portion of protuberance 11 just is the height L of protuberance 11 to the length of the vertical line that hangs down in the surface of base material portion 10.
In addition, in Fig. 2, because the border of base material portion 10 and protuberance 11 is clear and definite, so the height L of protuberance 11 defines as described above, but under the indefinite situation in the border of base material portion 10 and protuberance 11, the height L of protuberance 11 defines as described below.
At first, determine the section (being designated hereinafter simply as " section of collector body ") of collector body thickness direction.The section of collector body is confirmed as comprising the top portion of protuberance, and the area of protuberance section reaches maximum.
In the section of collector body, between adjacent protuberance, there is concave surface.In 2 concave surfaces of the both sides that are in 1 protuberance, obtain respectively perpendicular to the most recessed point on the direction on collector body surface.Connect 2 points the most recessed and describe straight line.By the mid point of this straight line, with respect to describing vertical straight line with the direction of collector body Surface Vertical, with it as datum line.The length of the vertical line that hangs down to datum line from the top portion of protuberance just is the height L of protuberance.
In addition, so-called 0.3L height, be meant from the top portion of protuberance 11 on the vertical line that the surface or the above-mentioned datum line of base material portion 10 hangs down, be the position of 0.3L apart from the surface of base material portion 10 or the length of said reference line.The diameter D of so-called protuberance 11 0.3, be meant section width at the locational protuberance 11 of 0.3L height.The section width of so-called protuberance 11 is meant the width (length) on the direction of the base material portion that is parallel to 10 surfaces in the section of protuberance 11 or above-mentioned datum line as mentioned above.Similarly, at the diameter D of the protuberance 11 of 0.8L height 0.8It also is section width at the locational protuberance 11 of 0.8L height.
Become above-mentioned formation by the section configuration that makes protuberance 11, expand the stress that between base material portion 10 and protuberance 11, produces thereby can disperse or relax the active material layer that the adhering on surface because of protuberance 11 carries.If D 0.3≤ D 0.8, then the stress that produces at protuberance 11 is owing to concentrate at the interface of base material portion 10 and protuberance 11 easily, so protuberance 11 often peels off from base material portion 10.
In addition, preferably at 0.5L diameter D highly 0.5With diameter D at the 0.3L height 0.3Ratio (D 0.5/ D 0.3) be below 0.98, more preferably 0.4～0.9.At this, so-called diameter D at the 0.5L height 0.5With above-mentioned same, be meant section width at the locational protuberance 11 of 0.5L height.If D 0.5/ D 0.3Surpass 0.98, then the shape of protuberance 11 approaches cylindric or the rounding frustum, thereby often produces the tendency that stress is concentrated at the interface of base material portion 10 and protuberance 11.Consequently, might improve the frequency that protuberance 11 is peeled off from base material portion 10.
In addition, at 0.8L diameter D highly 0.8With diameter D at the 0.5L height 0.5Ratio (D 0.8/ D 0.5) be preferably 0.4, more preferably 0.5～0.95.If D 0.8/ D 0.5Less than 0.4, then protuberance 11 becomes the very sharp shape of top ends, thereby has the top ends easy deformation, can not obtain the possibility of stability characteristic (quality).
The height L of protuberance 11 is not special to be limited, but is preferably 1～20 μ m, more preferably 3～10 μ m.During the height L less than 1 μ m of protuberance 11, the effect that often relaxes stress becomes insufficient.If the height L of protuberance 11 surpasses 20 μ m, then often protuberance 11 shared volume ratio in electrode integral body increases, thereby is difficult to guarantee practical high power capacity.
In addition, in the section of the thickness direction of collector body shown in Figure 21, straight line (or straight line of the concave surface 12 of expression and the protuberance 11 adjacency) angulation on the surface of the straight line of expression protuberance 11 sides and the base material portion 10 of expression and protuberance 11 adjacency is set at angle θ.In the present invention, at least 1 among the preferred angle θ is the obtuse angle, is the obtuse angle more than the 60 number % of angle θ more preferably.Be preferably more than 90 ° but as the angle of the angle θ at obtuse angle less than 160 °, more preferably greater than 92 ° but less than 145 °.In addition, with the concave surface 12 uneven situations of protuberance 11 adjacency under, the straight line of the side of expression protuberance 11 and above-mentioned datum line angulation are set at angle θ.In addition, the line in the side of representing protuberance 11 is under the situation of curve, then obtains the tangent line at the curve of 0.5L position highly, and this tangent line and the straight line on expression base material portion 10 surfaces or above-mentioned datum line angulation are set at angle θ.
In addition, the height L of protuberance 11, diameter D 0.3, diameter D 0.5, diameter D 0.8With angle θ is respectively 5 protuberances 11 arbitrarily to be measured, resulting 5 measured values are averaged and obtain.
Along with protuberance 11 to bearing of trend development, the section configuration of protuberance 11 is so long as the coniform shape that the section width of protuberance 11 reduces, just not special restriction, but D more preferably 0.8＞D 0.3Fig. 3 is the longitudinal section of section configuration of the protuberance 13a～13g of other execution mode of expression.
In Fig. 3, straight line 10a represents the border on protuberance 13a～13g and not shown base material portion 10 surfaces.In addition, protuberance 13a～13g is generically and collectively referred to as protuberance 13.Shown in Fig. 3 (a)～(g), in the section configuration of protuberance 13, the line of the side of expression protuberance 13 both can be a straight line, also can be curve.In addition, curve both can protrude towards not shown base material portion 10 surfaces, also can protrude towards the bearing of trend of protuberance 13.In the section of protuberance 13, the line of the top ends of expression protuberance 13 both can be a straight line, also can be curve.Consider that from the angle that improves effect of the present invention the section configuration of protuberance 13 is preferably especially hangs bell or spindle-type shown in Fig. 3 (g).In protuberance 13g, from the side to the curve on base material portion 10 surfaces owing to protrude, so the stress that is attached on the border 10a of protuberance 13 and base material portion 10 can disperse effectively towards base material portion 10 surfaces.
From directly over the not special restriction of shape (shape of orthographic drawing) when seeing protuberance 11.For example, can list circle, ellipse, polygonal, fan-shaped, crescent etc.As polygonal, preferably triangle, square, pentagon, hexagon etc. particularly preferably are equilateral triangle, positive square, positive pentagon, regular hexagon etc.
In addition, at least a portion on protuberance 11 surfaces, also can form the thrust that extends to the outside of protuberance 11 from protuberance 11 surfaces.This thrust both can be 1, also can be a plurality of.In addition, thrust is preferably less than protuberance 11.
Protuberance 11 does not limit especially in the arrangement on base material portion 10 surfaces, but preferably arranges with the pattern of rule.Thus, can be in electrode configuration space that the swelling stress of active material is relaxed regularly.And then, can prevent the distortion of electrode effectively.In addition, when the active material layer of institute's appendix expands on protuberance 11, can reduce the contact between the active material layer of adjacency.Protuberance 11 is preferably in base material portion 10 and for example arranges with patterns such as staggered clathrate, chessboard trellis.
The not special restriction of the manufacture method of collector body 1, but preferably make by compression process not.So-called " not compression process " is meant not at protuberance 11 from compression stress such as additonal pressure on one's body but utilize the plastic deformation etc. of material to form the processing method of protuberance 11.As the advantage of compression process not, can list the following aspects.
The durability of resulting collector body 1 is improved, and can prevent protuberance 11 peeling off from the base material portion 10.Meanwhile, when when forming protuberance 11 or on protuberance 11 surfaces, forming active material layer, can prevent from local distortion and bending etc. to take place in base material portion 10.In addition, protuberance 11 surface is improved with the bond strengths of active material layer, in the formation operation of active material layer, slitting when electrode is made are cut manufacturing procedure etc., can suppress active material layer peeling off from protuberance 11 surfaces significantly.
Therefore, be loaded in the battery, even use the battery that reduction is also less and reliability is high of performance between then can obtaining for a long time if will on collector body 1, be formed with the electrode of active material layer.
In addition, the top portion of the protuberance 11 on the direction that protuberance 11 extends is under the situation on plane, and this plane is owing to be compression process not, thereby can not be subject to processing the influence of strain etc., therefore, can keep collector body before the compression process not with the surface roughness of material web.Therefore, if collector body is adjusted into only scope with the surface roughness of material web, then after protuberance 11 forms, can the adjustment form surface roughness and can high accuracy and easily form active material layer.In addition, collector body is easy with the adjustment of the surface roughness of material web.
As the instantiation of compression process not, for example can list utilization has the roller of recess on the surface processing method (hereinafter referred to as " roller processing method "), processing method, resist processing method etc.Wherein, preventing aspect protuberance 11 the peeling off from the base material portion 10, preferably roller processing method and etching and processing method.In addition, making with high rate/low cost production aspect the collector body 1, preferably the roller processing method.
According to the roller processing method, use the roller that is formed with recess on the surface, mechanically collector body is carried out pressure processing with material web, make the collector body raw material produce plastic deformation with sheet segment ground, just can produce collector body 1 thus.In the case, corresponding with the recess 16 that is disposed at roller surfaces, on collector body at least one face, be formed with protuberance 11 with material web.
Fig. 4 is illustrated in the formation of employed roller 15 in the roller processing method.Fig. 4 (a) is the stereogram of the outward appearance of expression roller 15.Fig. 4 (b) is the stereogram that amplifies the surf zone 15a of the roller 15 shown in the presentation graphs 4 (a).Fig. 5 is the stereogram of the formation of wanting portion that expression contains the collector body manufacturing installation 20 of roller shown in Figure 4 15.Fig. 6 is the longitudinal section of explanation by the plastic deformation of roller processing method generation.
On the surface of roller 15, be formed with a plurality of recesses 16.Be under the situation of formpiston with protuberance 11, recess 16 also can form roughly the former corresponding to the shape of protuberance 11.
Recess 16 preferably will form coniform shape perpendicular to the section on the direction on roller 15 surfaces (being designated hereinafter simply as " recess section ").This coniform shape is from the bottom surface 16a of the recess 16 opening portion 16b to the recess 16 on roller 15 surfaces, and the width of recess section on the direction that is parallel to roller 15 surfaces (perpendicular to the direction of the radial direction of roller 15) slowly or the shape that increases continuously.By making the recess section become coniform shape, can easily form D 0.3＞D 0.8Protuberance 11.Form the recess 16 of coniform shape about section, its side tilts with respect to the direction with roller 15 Surface Vertical.By suitably selecting the angle of inclination of side, can D will be compared 0.5/ D 0.3With than D 0.8/ D 0.5Be adjusted into desirable value.
In addition, the Pareto diagram of the recess 16 on roller 15 surfaces is as follows in the present embodiment.Will be with spacing P on the long side direction of roller 15 1The row that connect a plurality of recesses 16 are set at 1 capable unit 17.A plurality of capable unit 17 at the circumferencial direction of roller 15 with spacing P 2Arrange.Spacing P 1With spacing P 2Can set up arbitrarily.In addition, in 1 capable unit 17 and the capable unit 17 that is adjacent, recess 16 is arranged in the mode that the long side direction at roller 15 takes place to be offset.In the present embodiment, recess 16 is 0.5P in the skew of long side direction 1, but the present invention is not limited thereto, can set arbitrarily.In addition, the Pareto diagram of recess 16 also is not limited to the Pareto diagram shown in Fig. 4 (b), can adopt various Pareto diagrams.
In order to form recess 16,, can from common recess formation method, suitably select optimal method to be used according to various conditions such as the diameter of the material of roller, recess, concave depth.As recess formation method, for example can list etching method, sand-blast, edm, laser processing etc.In these methods, preferably laser processing.According to laser processing, can form the finest recess with accurate Pareto diagram.As the employed laser of laser processing, for example can list carbon dioxide laser, YAG laser, excimer laser etc.The metal rolls etc. that the roller that forms recess 16 can use metal rolls and have coating layer.As the material of metal rolls, for example can list stainless steel, SCM steel etc.Coating layer for example contains at least a kind in alumina, titanium dioxide, chromium oxide, zirconia, silicon nitride, aluminium nitride, titanium nitride, tungsten carbide, carborundum, the aluminium carbide etc.So, can obtain roller 15.
Roller 15 for example is loaded in the collector body manufacturing installation 20 shown in Figure 5, is used to the making of collector body 1.Collector body manufacturing installation 20 comprises compression joint mechanism 21 and not shown material web conveying mechanism.
Compression joint mechanism 21 comprises 2 rollers 15.Each roller 15 is set to: can be subjected to the support of not shown driving mechanism around the mode that axle center rotation drives, the axle center of roller is parallel to each other, and is crimped on mutually and forms crimping together and vise the 21a of portion.In addition, each roller 15 is configured to: recess 16 vises portion 21a place in crimping, and is mutually opposed in identical position with the separation of material web by collector body.When collector body vises the 21a of portion with material web by crimping, then, produce local plastic deformation with the material web surface, thereby form protuberance 11 at collector body according to the Pareto diagram of the recess 16 on roller 15 surfaces.
The material web conveying mechanism vises the 21a of portion to the crimping of 2 rollers 15 and supplies with the collector body material web.The material web conveying mechanism for example comprises sends roller and a plurality of conveying roller.Collector body batches with material web and is sending on the roller.Conveying roller will vise the 21a of portion with material web to crimping and carry from sending collector body that roller sends.According to collector body manufacturing installation 20, make collector body vise the 21a of portion in the crimping of 2 rollers 15 and pass through with material web, just can obtain collector body 1 thus.Resulting collector body 1 is for example batched roller and is batched.
In addition, the rotating speed of crimping pressure that the degree of the plastic deformation of the 21a of portion for example can be by suitably selecting the collector body raw material to vise the 21a of portion with material and thickness, the crimping of thin slice, roller 15 is vised in crimping, the collector body raw material carried by the material web conveying mechanism regulates and control with the transporting velocity of thin slice etc.
The collector body that vises among the 21a of portion with regard to crimping based on Fig. 6 further is described in detail with the plastic deformation of material web below.Fig. 6 is the longitudinal section that the plastic deformation of being undertaken by the roller processing method is described.Fig. 6 (a) is that the expression collector body just has been supplied to the longitudinal section that the state behind the 21a of portion is vised in crimping with material web 23.To be the expression collector body vise the longitudinal section of the state that carries out among the 21a of portion with the plastic deformation on material web 23 surfaces in crimping to Fig. 6 (b).Fig. 6 (c) is the longitudinal section that vises the collector body 1 behind the 21a of portion by crimping.
Shown in Fig. 6 (a), the inlet that collector body vises the 21a of portion with material web 23 in crimping has thickness t.This material web 23 contacts with the surface of 2 rollers 15 and is pressurized.Then, shown in Fig. 6 (b), the part that contacts with the tabular surface of roller 15 in the material web 23 is compressed and becomes thickness t 1t 1Compare t 0Little.In contrast, in the material web 23 with the recess 16 opposed parts of roller 15 owing to do not pressurizeed, be compressed and plastic deformation take place so be accompanied by contact portion around the above-mentioned mutually opposed part.Consequently, swell above-mentioned mutually opposed part outside to material web 23 in the space of recess 16, thereby form protuberance 11.That is, protuberance 11 can not be subjected to the compression that produced by pressurization, just by plastic deformation promptly not compression process form.
Shown in Fig. 6 (c), protuberance 11 is owing to form by compression process not, so on the bearing of trend of protuberance 11, the plane 11a of the top ends of protuberance 11 can not be subject to processing the influence of strain etc., but keep surface state and the plane precision of collector body same as before with material web 23.
The side of protuberance 11 also has the surface state that is similar to collector body usefulness material web 23.On the other hand, the concave surface 12 that exists between adjacent protuberance 11 is owing to be compressed processing, thus have with collector body with the different surface state of material web 23.In addition, the maximum ga(u)ge t of collector body 1 2Be the length between the top ends plane 11a of the protuberance 11 that forms on the two sides of the thickness direction of collector body 1.The maximum ga(u)ge t of collector body 1 2Thickness t greater than original material web 23 0In addition, thickness t 0With maximum ga(u)ge t 2Between relation for example can adjust by the moulding pressure of suitably selecting crimping to vise the 21a of portion.
In the collector body 1 that obtains with the roller processing method, between base material portion 10 and protuberance 11, there is not the interface, exist at least 1 to have roughly the same crystalline state and 11 continuous zones from base material portion 10 to protuberance.If with the section of this collector body 1 thickness direction of electron microscope observation, then at least a portion of this section, have zone with roughly the same crystalline state, this zone cross over base material portion 10 and protuberance 11 both and be connected incessantly halfway.So long as observe, just can't see the crystalline state at expression junction surface in this zone with electron microscope.By adopting such formation, can significantly prevent protuberance 11 peeling off from the base material portion 10, and then significantly prevent active material layer peeling off from the protuberance 11.
In addition, according to the roller processing method, can be easily, with low-cost and make collector body 1 continuously.Especially, form coniform shape with protuberance 11 sections or recess 16 sections and combine, the roller 15 after protuberance 11 forms and the fissility of collector body 1 are good, so defect rate is very low.Therefore, this method is being good aspect the property produced in batches.
In addition, in the roller processing method,, similarly also can obtain collector body of the present invention even use the mould that is formed with recess on the surface to replace being formed with the roller of recess on the surface.The formation of mould upper recess can with form recess at roller surfaces and similarly implement.In addition, also can design the mould that has recess on the surface.
According to the etching and processing method of compression process method not of the conduct beyond the roller processing method,, just can make collector body 1 by carrying out etching with predetermined pattern on material web at collector body.As engraving method, for example can use laser, chemical reagent etc.The collector body 1 that obtains with this method also contains at least 1 and does not have the interface between base material portion 10 and protuberance 11, have roughly the same crystalline state and 11 connect continuously and the zone that exists from base material portion 10 to protuberance.Therefore, protuberance 11 possibility of peeling off from base material portion 10 becomes very low.
In addition, according to the resist processing method, at first form the resist pattern on base material portion 10 surfaces.Subsequently, when the base material portion 10 that is formed with this corrosion-resisting pattern is implemented plating or electrophoretic painting, then form protuberances 11 on base material portion 10 surfaces.In the method, between base material portion 10 and protuberance 11, often form discontinuous interface.
Fig. 7 is the longitudinal section of formation that schematically illustrates the collector body 25 of other execution mode.Collector body 25 is similar to collector body 1, for corresponding part mark same reference marks and omission explanation.Collector body 15 is characterised in that: comprise base material portion 10 and protuberance 11, protuberance 11 forms at the single face of the thickness direction of base material portion 10.Like this, protuberance 11 also can form at the single face of the thickness direction of base material portion 10.
Based on Fig. 8 the manufacturing that collector body 25 adopts the roller processing method to carry out is described below.Fig. 8 is the longitudinal section of the plastic deformation carried out of employing roller processing method of other execution mode of explanation.It is the longitudinal section of the manufacture method of explanation collector body 25.Fig. 8 (a) is that the expression collector body just has been supplied to the longitudinal section that the state after the portion 28 is vised in crimping with material web 23.Fig. 8 (b) is illustrated in the longitudinal section that the state of the plastic deformation of carrying out collector body usefulness material web 23 surfaces in the portion 28 is vised in crimping.Fig. 8 (c) is the longitudinal section that vises the collector body 25 after the portion 28 by crimping.
In the operation shown in Fig. 8 (a), the crimping in collector body manufacturing installation 26 is vised portion 28 and is supplied with collector body material web 23.At this moment, collector body has thickness t with material web 23.Collector body manufacturing installation 26 vises in the middle of 2 rollers of portion 28 forming crimping, and one is roller 15, and another is a roller 27, in addition, has the formation identical with collector body manufacturing installation 20.Roller 27 is to have an even surface and do not form the roller of recess.
In the operation shown in Fig. 8 (b), collector body pressurizes at thickness direction with material web 23.And collector body is divided into recess 16 opposed noncontact faces with roller 15 with the surface of material web 23, be present in noncontact face around and the contact-making surface that contacts with the surface of roller 15 or roller 27.Contact-making surface is subjected to moulding pressure and is compressed processing, forms base material portion 10.The thickness of base material portion 10 becomes t 1Thickness t 1Less than thickness t 0On the other hand, noncontact face is accompanied by the compression process of contact-making surface and plastic deformation takes place, and swells towards the bottom surface of recess 16, thereby forms protuberance 11.That is, protuberance 11 forms by compression process not.
In the collector body 25 shown in Fig. 8 (c), protuberance 11 is owing to form by compression process not, so on the bearing of trend of protuberance 11, the plane 11a of the top ends of protuberance 11 keeps the surface state of collector body with material web 23 same as before.The side of protuberance 11 also has the surface state that is similar to collector body usefulness material web 23.On the other hand, the concave surface 12 that between adjacent protuberance 11, exists and base material portion 10 with the surperficial 12a face opposition side that is formed with protuberance 11 owing to be compressed processing, so have with collector body with the different surface state of material web 23.In addition, the surperficial 12a almost parallel of the plane 11a of the top ends of protuberance 11 and the opposition side of base material portion 10, the interval between plane 11a and the surperficial 12a is maximum ga(u)ge t 2Greater than the thickness t of original collector body with material web 23 0
[electrode]
Electrode of the present invention is characterised in that: comprise collector body of the present invention and active material layer.
Collector body of the present invention as mentioned above.
Active material layer preferably contains a plurality of columnar-shaped particles.Columnar-shaped particle contains active material, and is formed from least a portion on collector body surface and extends to the outside of collector body.By adopting active material layer to contain the formation of a plurality of columnar-shaped particles, relax the swelling stress of active material easily.The shape of columnar-shaped particle is not special to be limited, shapes such as for example preferably cylindric, circular cone shape, rounding frustum, prism-shaped, prismatic platform shape, chamfered edge pylon shape.In addition, active material layer forms on surface or two surfaces of collector body thickness direction, but for the high capacity of the battery seeking finally to obtain, preferably forms on two surfaces.In addition, the thickness of active material layer (height of columnar-shaped particle) can be the thickness that can allow because of this degree of influence that expansion produced of active material.
Fig. 9 is the longitudinal section that schematically illustrates the formation of electrode 30 of the present invention.Electrode 30 is general names of electrode 30a, 30b, 30c, 30d, 30e, comprises collector body 31 and as the columnar-shaped particle 32 of active material layer.Collector body 31 is similar to collector body 1, about corresponding part mark identical reference marks and omission explanation.Collector body 31 is formed on the two sides this point of thickness direction of base material portion 10 identical with collector body 1 at protuberance 11.On the other hand, collector body 31 is with the dissimilarity of collector body 1: the protuberance 11 on base material portion 10 two sides is not to be in Jie by base material portion 10 on the opposed position, but is configured in the mode that skew takes place for protuberance 11 and another surperficial protuberance 11 of a face.Certainly, also can use collector body 1 to replace collector body 31.
Columnar-shaped particle 32 is general names of columnar-shaped particle 32a, 32b, 32c, 32d, 32e.Columnar-shaped particle 32a shown in Fig. 9 (a) is formed: extend the whole outside towards collector body 31 of the plane 11a (being designated hereinafter simply as " plane 11a ") of the top ends from the bearing of trend of protuberance 11.Columnar-shaped particle 32b shown in Fig. 9 (b) is formed: extend to the outside of collector body 31 from the part of plane 11a.Columnar-shaped particle 32c, 32d shown in Fig. 9 (c) and Fig. 9 (d) are formed: the part of the side 11b (being designated hereinafter simply as " side 11b ") from the bearing of trend of whole of plane 11a and protuberance 11 is extended to the outside of collector body 31.Columnar-shaped particle 32e shown in Fig. 9 (e) is formed: extend to the outside of collector body 31 from the plane 11a of protuberance 11 and side 11b whole and the part of concave surface 12.
So, columnar-shaped particle 32 can form at least a portion of the plane of protuberance 11 11a.In addition, columnar-shaped particle 32 can form at least a portion of at least a portion of the plane of protuberance 11 11a and side 11b.Moreover columnar-shaped particle 32 can form at least a portion of at least a portion of at least a portion of the plane of protuberance 11 11a and side 11b and concave surface 12.
Columnar-shaped particle 32 for example can form according to common film forming methods such as vacuum vapour deposition, sputtering method, chemical vapor deposition (CVD) methods.According to vacuum vapour deposition,,, thereby form columnar-shaped particle 32 by oblique foreign side evaporation active material steam from collector body 31 surfaces for example for collector body 31.At this moment and since the incident portion of active material steam be subjected to covering of protuberance 11, so the predetermined portions of active material steam on collector body 31 surfaces optionally carries out evaporation.
Figure 10 is the cutaway view of formation that schematically illustrates the electrode 35 of other execution mode.Electrode 35 comprises collector body 1 and active material layer 36.Electrode 35 is characterised in that and comprises active material layer 36.
Active material layer 36 contains a plurality of columnar-shaped particles 37.Columnar-shaped particle 37 is characterised in that: tilt with respect to the direction N with the Surface Vertical of collector body 1.That is, columnar-shaped particle 37 is formed: direction (hereinafter referred to as " direction of growth D ") angulation that extends to the outside from the surface of collector body 1 perpendicular to the direction N and the columnar-shaped particle 37 on collector body 1 surface is θ 1
In addition, if the surface of collector body with perusal, then is a tabular surface, if but observe from microcosmic, then have concavo-convex.Therefore, in this manual, if even it also is smooth that the surface of collector body is observed from microcosmic, then so-called direction perpendicular to the collector body surface is just as its implication.On the other hand, be to have a concavo-convex surface if the surface of collector body is observed from microcosmic, then under situation about collector body being positioned on the horizontal plane, will be perpendicular to the direction of this horizontal plane as direction perpendicular to the collector body surface.
The direction of growth D2 of columnar-shaped particle 37 can carry out suitable adjustment.In order to form columnar-shaped particle 37, for example can use not shown vacuum deposition apparatus.This vacuum deposition apparatus comprises: the collector body fixed station, and it is supported in freely mode of rotation and fixing collector body; And target, it is built up in the vertical lower of collector body fixed station, and supplies with the steam of active material to the vertical direction top.In this vacuum deposition apparatus, with collector body 1 towards vertical direction below and be fixed on the collector body fixed station.Then, suitably adjust the surface of collector body 1 and the angle of horizontal plane on one side, supply with the steam of active material on one side by target, just can form columnar-shaped particle 37 by this.At this moment, the direction of growth D2 of columnar-shaped particle 37 is decided with the horizontal plane angulation by the collector body surface.In addition, the direction of growth D2 of so-called columnar-shaped particle 37, if observe from microcosmic, the prolonging direction of the active material crystal grain (grain) that is contained for columnar-shaped particle 37 then.
In addition, columnar-shaped particle 37 is designed to: and the columnar-shaped particle 37 of adjacency between have the space and isolate.Under the effect in this space, the swelling stress of active material is relaxed.
In the present embodiment, the side of the direction that columnar-shaped particle 37 extends to the outside from the surface of collector body 1 (hereinafter referred to as " direction of growth ") roughly is level and smooth, but the present invention is not limited thereto, also can have concavo-convex.In addition, though columnar-shaped particle 37 is expressed as 1 shot-like particle, the present invention is not limited thereto, also can be that a plurality of small column piece heaps are built and the shot-like particle of formation.In the case, the border between the column piece of the side of columnar-shaped particle 37 becomes bend.The column piece both can be all to inclined, also can be that each column piece tilts to different directions.
The not special restriction of the shape of columnar-shaped particle 32,37.Columnar-shaped particle 32,37 shapes of being grown depend on the shape of plane, the top 11a of protuberance 11.For example, be that the shape of columnar-shaped particle 32,37 becomes shapes such as cylinder, the frustum of a cone, rounding frustum according to the difference of its formation condition under the situation of circle at the plane, top of protuberance 11 11a.Columnar-shaped particle 32,37 is along its length direction, and thickness also can change.On at least a portion on protuberance 11a surface, but the part beyond protuberance 11 also can its part of appendix by appendix for columnar-shaped particle 32,37.Appendix the part of columnar-shaped particle 32,37 and can be controlled according to the surface and the horizontal plane angulation of collector body 1,31 in the height of protuberance 11, the above-mentioned vacuum deposition apparatus.
The thickness T of active material layer 36 is carried out suitable selection according to design performance of the battery that finally obtains etc., but is preferably about 3～40 μ m, and more preferably 5～30 μ m are preferably 10～25 μ m especially.During the thickness T less than 3 μ m of active material layer, active material shared ratio in cell integrated is reduced, the energy density of battery reduces.In addition, if the thickness T of active material layer 36 surpasses 40 μ m, then the stress in the interface of collector body 1 and columnar-shaped particle 37 increases, and the distortion of collector body 1 etc. often takes place.At this, the thickness T of active material layer be just arbitrarily 10 columnar-shaped particles 37 obtain separately height, and its measured value averaged obtain.The height of so-called columnar-shaped particle 37 is the length from the vertical line that hangs down to collector body 1 surface or above-mentioned levelling line away from the position of collector body 1 surface or above-mentioned levelling line of columnar-shaped particle 37.
Active material layer 36 considers preferably have predetermined porosity from the angle of the stress that the expansion that relaxes because of active material causes.The porosity P of active material layer can obtain according to the real density of weight, thickness and the active material of the active material layer of certain area.In addition, in the method for using the porosimeter that is pressed into based on gas absorption or mercury etc., can measure porosity P more exactly.
The selection that degrees of expansion when the porosity P of active material layer 36 embeds lithium according to active material etc. are in addition suitable, but be preferably about 10～70%, more preferably 30～60%.It is generally acknowledged that as long as porosity P is more than 10% then the stress that produces for the expansion and the contraction that relax because of columnar-shaped particle 37 is just enough, and can granular particle 37 be contacted with electrolyte with sufficient level.In addition, be 30～60% if make porosity P, the capacity in the time of then for example can suppressing to discharge and recharge at a high speed reduces.In addition, even porosity P surpasses 70%,, also can use preferably as electrode according to the difference of battery use.
In addition, the present invention is under the situation of negative electrode active material layer at active material layer when the diameter of the thickness of measuring the porosity of active material layer, active material layer, columnar-shaped particle and section configuration etc., and preferred active material layer is in complete discharge condition.So-called discharge condition fully is meant that active material contains lithium that is equivalent to irreversible capacity and the state that does not contain the lithium that is equivalent to reversible capacity (reversible capacity is 0 state).The volume of the negative electrode active material layer in the battery that complete discharge condition is equivalent to finish is minimum state.
In addition, also can under the state that does not contain the lithium that is equivalent to irreversible capacity, measure, revise resulting measured value and obtain the value of complete discharge condition.For example, when asking calculation porosity P, carry out following correction operation.The porosity P that does not contain the active material layer of lithium fully BFor example use the mercury porosimeter to measure.Secondly, measure complete discharge condition active material layer volume and do not contain the volume of the active material layer of lithium fully, obtain volume differences Δ V.The porosity P of the active material layer of complete discharge condition AAccording to P A=P B-Δ V and obtaining.
In addition, at active material layer is under the situation of positive electrode active material layer, and the measurement of the diameter of the porosity of active material layer, the thickness of active material layer, columnar-shaped particle and section configuration etc. is preferably to be carried out the active material layer under the state after just discharging and recharging for the first time.In addition, also can under the state after not being just to have discharged and recharged for the first time, measure, revise resulting measured value and obtain value under the state after just discharging and recharging for the first time.For example, at first for example use the mercury porosimeter to measure the porosity P of the active material layer that does not does not discharge and recharge fully YSecondly, the volume of the volume of the active material layer under the state after measurement just discharges and recharges for the first time and the active material layer that does not does not discharge and recharge is fully obtained volume differences Δ V.The porosity P of the active material layer under the state after just discharging and recharging for the first time XCan be according to P X=P Y-Δ V obtains.
Under the situation that electrode of the present invention uses as negative pole, active material is preferably and contains the compound that is selected from least a kind alloy system negative electrode active material among silicon, tin, germanium and the aluminium and/or contains the alloy system negative electrode active material.The compound that contains the alloy system negative electrode active material is at least a kind that is selected among at least a kind alloy, oxide and the sulfide that contains the alloy system negative electrode active material.The alloy that contains the alloy system negative electrode active material is the alloy more than 2 kinds that contains above-mentioned alloy system negative electrode active material.As the oxide that contains the alloy system negative electrode active material, for example can list SiO x(0＜x＜2), SnO x(0＜x＜2).At SiO xIn, the x that contains ratio of expression oxygen considers from practical angle, is preferably 0.01～1.In addition, as the sulfide that contains the alloy system negative electrode active material, for example can list SiS x(0＜x＜2), SnS etc.Among them, preferably the alloy system negative electrode active material, contain the oxide of alloy system negative electrode active material etc., particularly preferably be silicon, SiO xDeng.In addition, in active material, for example also can be to the embedding of lithium ion with take off on the degree that embedding do not exert an influence and contain impurity such as Al, Fe, Ca.
At electrode of the present invention is that active material is preferably lithium-containing transition metal oxide under the situation of positive pole.As lithium-containing transition metal oxide, not special restriction can not used material known, but LiCoO preferably 2, LiNiO 2, LiMn 2O 4, LiMnO 2, LiNi aCo 1-aO 2, LiNiCo bMn cO 2(a+b+c=1) and make modified material of solutionizing among them such as aluminium, magnesium etc.In addition, MnO 2Also can be used as the active material use Deng the metal oxide that does not contain lithium.Among them, consider from the angle of high capacity and practicability, preferably LiCoO 2Deng.
[rechargeable nonaqueous electrolytic battery]
Rechargeable nonaqueous electrolytic battery of the present invention comprises electrode of the present invention, its nonaqueous electrolyte to electrode and lithium-ion-conducting.That is, rechargeable nonaqueous electrolytic battery of the present invention is the nonaqueous electrolyte lithium secondary battery.Contain under the situation of electrode of the present invention as negative pole the not special restriction of anodal structure at rechargeable nonaqueous electrolytic battery of the present invention.In addition, contain under the situation of electrode of the present invention as positive pole the not special restriction of the structure of negative pole at rechargeable nonaqueous electrolytic battery of the present invention.In addition, electrode of the present invention is preferably used as negative pole.
Figure 11 is the exploded stereogram that schematically illustrates as the formation of the rechargeable nonaqueous electrolytic battery 40 of one of embodiments of the present invention.Rechargeable nonaqueous electrolytic battery 40 comprises electrode group 41, positive wire 42, negative wire 43, insulation board 44, hush panel 45, packing ring 46 and battery container 47.
Electrode group 41 comprises positive pole 50, negative pole 51 and barrier film 52, positive pole 50, barrier film 52, negative pole 51 and barrier film 52 is merged by this order stack reel, and forms helical form.Electrode group 41 contains not shown electrolyte.
Anodal 50 is that electrode of the present invention or negative pole 51 are under the situation of electrode of the present invention, contains not shown positive electrode collector and positive electrode active material layer.
As positive electrode collector, can use in this field material commonly used, for example can list the metal forming that constitutes by aluminium, aluminium alloy, stainless steel, titanium etc., nonwoven fabrics etc.The not special restriction of the thickness of positive electrode collector, but be preferably 5 μ m～30 μ m.
Positive electrode active material layer is formed on the face or two faces of thickness direction of positive electrode collector, contains positive active material, and contains conductive agent and binding agent as required.As positive active material, can use above-mentioned illustrative lithium-containing transition metal oxide, MnO 2Deng the metal oxide that does not contain lithium etc.
As conductive agent, can use the material commonly used in this field, for example can list: graphite-like, as native graphite and Delanium; The carbon black class is as acetylene black, section's qin carbon black, channel carbon black, oven process carbon black, dim, thermal black etc.; The conducting fibre class is as carbon fiber and metallic fiber etc.; The metal dust class is as fluorocarbons and aluminium etc.; Conductivity whisker class is as zinc oxide and potassium titanate etc.; Conductive metal oxide is as titanium oxide etc.; And the organic conductive material, as crystalline 1,2-phenylene derivatives etc.
As binding agent, for example can list: Kynoar (PVDF), polytetrafluoroethylene, polyethylene, polypropylene, aromatic polyamide resin, polyamide, polyimides, polyamide-imides, polyacrylonitrile, polyacrylic acid, polymethyl acrylate, polyethyl acrylate, the own ester of polyacrylic acid, polymethylacrylic acid, polymethyl methacrylate, polyethyl methacrylate, the own ester of polymethylacrylic acid, polyvinyl acetate, polyvinylpyrrolidone, polyethers, polyether sulfone, hexafluoro polypropylene; butadiene-styrene rubber; carboxymethyl cellulose; contain the rubber particles binding agent of acrylic ester unit etc.In addition, also can use by be selected from tetrafluoroethene, hexafluoroethylene, hexafluoropropylene, perfluoroalkyl vinyl ether, vinylidene, chlorotrifluoroethylene, ethene, propylene, five fluorine propylene, methyl fluoride vinyl ethers, acrylic acid, hexadiene, contain reactive functional groups acrylate monomer, contain copolymer that the monomeric compound more than 2 kinds in the acrylate oligomer etc. of reactive functional groups constitutes as binding agent.
Anodal 50 for example can adopt following method to make.At first, make mixing such as positive active material and the conductive agent that adds as required, binding agent and be dispersed in the decentralized medium, thereby mix the anode mixture slurry.Decentralized medium for example can use the decentralized medium commonly used in this field such as N-N-methyl-2-2-pyrrolidone N-.Positive active material etc. in decentralized medium mixing and when disperseing, for example can use common dispersion machines such as planetary stirring machine.The anode mixture slurry that obtains like this is coated on the single face or two sides of positive electrode collector, carries out drying and roll into preset thickness, just can form positive electrode active material layer thus, thereby obtain anodal 50.
At negative pole 51 is that electrode of the present invention or anodal 50 is under the situation of electrode of the present invention, contains not shown negative electrode collector and negative electrode active material layer.
As negative electrode collector, can use in this field material commonly used, for example can list by copper, nickel, iron and contain metal forming that at least a kind the alloy etc. of these elements constitutes, metallic film etc.Among them, the preferably metal forming that constitutes by copper or copper alloy, metallic film etc.As copper alloy, can as this specification is before illustrative, use copper alloy.With the metal forming that adopts copper and copper alloy is example, for example can list electrolytic copper foil, cathode copper Alloy Foil, rolled copper foil, copper alloy foil, calendering copper alloy foil and they have been implemented the paper tinsel etc. of asperities processing.As the paper tinsel of implementing the asperities processing, preferably electrolytic copper foil, rolled copper foil, copper alloy foil etc.The not special restriction of the thickness of the base material portion of negative electrode collector, but be preferably 5 μ m～100 μ m, more preferably 8～35 μ m.When the thickness less than 5 μ m of the base material portion of negative electrode collector, often the mechanical strength of negative electrode collector becomes insufficient, and the operability when electrode is made reduces.In addition, the fracture of the electrode during battery charge etc. takes place easily.On the other hand,, then can guarantee mechanical strength, but negative electrode collector shared volume in electrode integral body increases, often can not realize the high capacity of battery fully if the thickness of the base material portion of negative electrode collector surpasses 100 μ m.
Negative electrode active material layer is formed on the face or two faces of the extremely electric body thickness direction of negative pole, contains positive active material, can also contain conductive agent, binding agent, thickener etc. as required.As negative electrode active material, for example can use silicon series composite materials such as graphite materials such as various native graphites and Delanium, silicide and alloy system negative electrode active material etc.As conductive agent, can use with positive electrode active material layer in the conductive agent identical materials of being added.As binding agent, also can use with positive electrode active material layer in the same material of binding agent that adds.Moreover, consider from improving the Receptive angle of lithium ion, can use Styrene-Butadiene rubber particles (SBR) and modification body thereof etc. as binding agent.
As thickener, can use material commonly used in this field.Wherein, preferably have material water-soluble and that under the form of the aqueous solution, have viscosity, for example can list cellulose-based resins such as carboxymethyl cellulose (CMC) and modification body thereof, poly(ethylene oxide) (PEO), polyvinyl alcohol (PVA) etc.In these materials, consider from dispersiveness, the thickening property equal angles of cathode agent slurry described later, particularly preferably be cellulose-based resin and modification body thereof.
Make mixings such as negative electrode active material and the conductive agent that adds as required, binding agent, tackifier and be dispersed in the decentralized medium, thereby mix the cathode agent slurry, in addition, negative pole 51 can similarly be made with positive pole 50.
As barrier film 52, can use in the field of rechargeable nonaqueous electrolytic battery material commonly used, for example use individually or compoundly that polyolefinic little porous membrane such as polyethylene, polypropylene is typical, and be preferred as an execution mode.More particularly, as barrier film 52, can list the multiple aperture plasma membrane that constitutes by synthetic resin.As synthetic resin, for example can list polyolefin such as polyethylene, polypropylene, aromatic polyamide resin, polyamide-imides, polyphenylene sulfide, polyimides etc.Multiple aperture plasma membrane for example has micro-porous film, nonwoven fabrics etc.In addition, barrier film 52 is portion or surface within it, also can contain thermal endurance fillers such as alumina, magnesium oxide, silica, titanium dioxide.In addition, also can on the two sides of barrier film 52 thickness directions or single face, set up refractory layer.Refractory layer for example contains above-mentioned thermal endurance filler and binding agent.Binding agent can use and the employed binding agent identical materials of positive electrode active material layer.In addition, the thickness of barrier film 17 is not special to be limited, but is preferably 10 μ m～30 μ m, more preferably 10～25 μ m.
As nonaqueous electrolyte, can use the electrolyte solution that in organic solvent, is dissolved with solute and contain solute and organic solvent and utilize macromolecular compound and make the polymer dielectric of its non-currentization or solid electrolyte etc.Under the situation of using electrolyte solution, preferably in barrier film 17, flood electrolyte solution.In addition, nonaqueous electrolyte also can contain additive except that solute, organic solvent and macromolecular compound.
Solute is selected according to oxidation-reduction potential of active material etc.Specifically,, solute commonly used in the field of lithium battery can be used, for example LiPF can be listed as solute 6, LiBF 4, LiClO 4, LiAlCl 4, LiSbF 6, LiSCN, LiCF 3SO 3, LiN (CF 3CO 2), LiN (CF 3SO 2) 2, LiAsF 6, LiB 10Cl 10, lower aliphatic carboxylic acid lithium, LiF, LiCl, LiBr, LiI, chloroborane base lithium, two (1,2-benzenediol (2-)-O, O ') borate lithium, two (2,3-naphthalenediol (2-)-O, O ') borate lithium, two (2,2 '-'-biphenyl diphenol (2-)-O, O ') borate family, (CF such as borate lithium, two (5-fluoro-2-hydroxyl-1-benzene sulfonic acid-O, O ') borate lithium 3SO 2) 2NLi, LiN (CF 3SO 2) (C 4F 9SO 2), (C 2F 5SO 2) 2NLi, tetraphenyl lithium borate etc.Solute can use a kind separately, or two or more kinds may be used as required.
As organic solvent, can use organic solvent commonly used in the field of lithium battery, for example can list ethylene carbonate (EC), propylene carbonate, butylene carbonate, vinylene carbonate, dimethyl carbonate (DMC), diethyl carbonate, methyl ethyl carbonate (EMC), dipropyl carbonate, methyl formate, methyl acetate, methyl propionate, ethyl propionate, dimethoxymethane, gamma-butyrolacton, gamma-valerolactone, 1, the 2-diethoxyethane, 1, the 2-dimethoxy-ethane, methoxy ethoxy ethane, trimethoxy-methane, oxolane, tetrahydrofuran derivatives such as 2-methyltetrahydrofuran, dimethyl sulfoxide (DMSO), 1,3-two oxa-pentanes, the 4-methyl isophthalic acid, two oxa-pentane derivatives such as 3-two oxa-pentanes, formamide, acetamide, dimethyl formamide, acetonitrile, propionitrile, nitromethane, Monoethylene Glycol (MEG) diethyl ether (ethyl monoglyme), phosphotriester, acetic acid esters, propionic ester, sulfolane, the 3-methyl sulfolane, 1,3-dimethyl-2-imidazolone, 3-methyl-2-oxazolidone, the propylene carbonate ester derivant, ether, diethyl ether, 1, the 3-N-morpholinopropanesulfonic acid lactone, methyl phenyl ethers anisole, fluorobenzene etc.Organic solvent can use a kind separately, or two or more kinds may be used as required.
As additive, for example also can contain vinylene carbonate, cyclohexyl benzene, biphenyl, diphenyl ether, vinyl ethylidene carbonic ester, divinyl ethylidene carbonic ester, phenyl ethylidene carbonic ester, diallyl carbonic ester, fluoroethylene carbonic ester, catechol carbonic ester, vinylacetate, ethylidene sulfite, propane sultone, trifluoro propylene carbonate, dibenzofurans, 2, additives such as 4-difluoroanisole, adjacent terphenyl, a terphenyl.Additive can use a kind separately, or two or more kinds may be used as required.
In addition, nonaqueous electrolyte also can mix above-mentioned solute in the mixture more than a kind or 2 kinds of following macromolecular material etc., it is used as solid electrolyte, and macromolecular material wherein comprises: poly(ethylene oxide), PPOX, poly phosphazene, polyaziridine, polyvinyl thioether, polyvinyl alcohol, Kynoar, polyhexafluoropropylene etc.In addition, also can mix with above-mentioned organic solvent and be used with gel.Moreover, also can be with lithium nitride, lithium halide, lithium oxysalt, Li 4SiO 4, Li 4SiO 4-LiI-LiOH, Li 3PO 4-Li 4SiO 4, Li 2SiS 3, Li 3PO 4-Li 2S-SiS 2, inorganic material such as phosphoric sulfide compound used as solid electrolyte.Under the situation of using solid electrolyte or gel-like electrolyte, also can make it replace these barrier films 17 to be configured between positive pole 50 and the negative pole 51.Perhaps, gel-like electrolyte also can be configured to barrier film 52 adjacent.
About positive wire 42, negative wire 43, insulation board 44, hush panel 45, packing ring 46 and battery container 47, can use material commonly used in the field of rechargeable nonaqueous electrolytic battery.
Rechargeable nonaqueous electrolytic battery 40 of the present invention for example can adopt following method to make.One end of positive wire 42 and negative wire 43 is electrically connected with the positive electrode collector of positive pole 50 and the negative electrode collector of negative pole 51 respectively.Electrode group 41 is accommodated in the inside of round-ended cylinder shape battery container 47 with insulation board 44.The other end of the negative wire 43 that will derive from the bottom of electrode group 41 is connected the bottom of battery container 47, then will be connected on the hush panel 45, in battery container 47, inject the not shown nonaqueous electrolyte of scheduled volume from the positive wire 42 that derive on the top of electrode group 41.Then, the peristome that the hush panel 45 that periphery is installed on packing ring 46 is inserted battery containers 47 carries out the inside bending of the peristome of battery container 47 ca(u)lk and seals, and just can obtain rechargeable nonaqueous electrolytic battery 40 thus.
Figure 12 is the cutaway view that schematically illustrates as the formation of the laminate type battery 55 of one of embodiments of the present invention.Laminate type battery 55 comprises positive pole 56, negative pole 57, barrier film 58, battery container 59, positive wire 60, negative wire 61 and sealing resin 62.Anodal 56 comprise positive electrode collector 66a and the positive electrode active material layer 56b that forms on a surface of the thickness direction of positive electrode collector 66a.Negative pole 57 comprises negative electrode collector 57a and the negative electrode active material layer 57b that forms on a surface of the thickness direction of negative electrode collector 57a.Positive pole 56 and negative pole 57 are set to by the separation of barrier film 58 opposed.That is, in laminate type battery 55 that positive pole 56, barrier film 58 and negative pole 57 is superimposed and stacked with this order, just form flat electrode group.Anodal 56, negative pole 57 and barrier film 58 have the formation same with the positive pole 50 of rechargeable nonaqueous electrolytic battery 40, negative pole 51 and barrier film 52 respectively.
Battery container 59 is the container-like component with 2 openings, and the electrode group is being taken in the portion space within it.2 openings of battery container 59 are situated between respectively and are sealed by sealing resin 62.One end of positive wire 60 is electrically connected with positive electrode collector 66a, and the other end is exported to the outside of battery 55 from an opening of battery container 59.One end of negative wire 61 is electrically connected with negative electrode collector 57a, and the other end is exported to the outside of battery 55 from another opening of battery container 59.In addition, in laminate type battery 55, also can use with rechargeable nonaqueous electrolytic battery 40 in same nonaqueous electrolyte.
So, rechargeable nonaqueous electrolytic battery of the present invention for example can adopt square battery, the cylinder battery with Wound type electrode group with Wound type electrode group, the various forms such as layer-built battery with cascade type electrode group.
Embodiment
Below enumerate embodiment, carry out specific description with regard to the present invention.
Embodiment 1
(1) making of collector body
Installation is formed with that a plurality of degree of depth are 8 μ m, roughly rounded and section configuration is that the ceramic roller of recess of coniform shape (bottom surface diameter 8 μ m, opening diameter 12 μ m) is as the roller 15 of collector body manufacturing installation 20 shown in Figure 5.Making as collector body is that the aluminium foil of 15 μ m vises the 21a of portion adding to depress by the crimping of collector body manufacturing installation 20 with the thickness of material web 23, carrying out compression process and non-compression process, thereby produces collector body shown in Figure 13 65.Figure 13 has schematically illustrated the formation as the collector body 65 of one of embodiments of the present invention.Figure 13 (a) is the vertical view of collector body 65.Figure 13 (b) is the longitudinal section of collector body 65.That is to say, be the cutaway view of thickness direction.
Resulting collector body 65 comprises that the base material portion 10 that is made of aluminium and the height that forms regularly on the two sides of the thickness direction of base material portion 10 are 5 μ m and roughly rounded protuberance 11, and is total thickness t 2It is the collector body of the band shape of 20 μ m.On Width (short side direction) X, be formed with protuberance 11 with spacing P 3Be arranged in the capable unit 17 of row.On long side direction Y, row unit 17 is with spacing P 4Be arranged in parallel.Moreover, be expert at unit 17 and the capable unit 17 that is adjacent in, each protuberance 11 is configured to be offset 0.5P on Width X 3Distance.The Pareto diagram of such protuberance 11 is owing to being that the tightst filling is arranged, so collector body 65 has sufficient durability for the tensile stress that is applied on the long side direction Y.Therefore, when collector body 65 is processed as positive pole, when the positive pole that will obtain is processed as the size that is suitable for battery sizes etc., can prevent the local deformation and the deflection that on collector body 65, produce.
For the collector body 65 that obtains, measure surface with surface roughometer as aluminium foil, the plane 11a of the top ends of result on the bearing of trend of protuberance 11 be with processing before the roughly equal surface roughness of aluminium foil.In addition, (SEM) observes protuberance 11 with scanning electron microscope, and the result has seen and processed the same tiny scratch of observed scratch on the preceding aluminium foil.On the other hand, compare before with processing protuberance 11, the surface roughness of concave surface 12 reduces, and the surface roughness of this surface roughness and ceramic roller is roughly equal.
Moreover, for collector body 65, having carried out resolving based on the crystal orientation of Electron Back-Scattered Diffraction style (EBSP) method, the result compares before observing protuberance 11 and concave surface 12 and processing, and crystal grain attenuates little.In addition, measure the result of the hot strength of positive electrode collector 65,, can infer that hot strength is improved under the effect based on the work hardening of compression process although, do not see the reduction of hot strength in the segment thickness attenuation of concave surface 12.
According to above analysis result, can think if on aluminium foil, implement above-mentioned processing, then keeping the not state of compression process with the opposed noncontact face of the recess of ceramic roller, and contact-making surface in addition is implemented compression process, shown in Figure 13 (b), this can obtain having the not collector body 65 of the protuberance 11 of the top ends plane 11a of compression process being compressed to have formed in the base material portion 10 of processing.
(2) Zheng Ji making
Will be as the cobalt acid lithium of 100 weight portions that obtain with the part of nickel and manganese displacement cobalt of positive active material, stir with double-arm mixer and mixing as the acetylene black of 2 weight portions of conductive agent and as 2 parts by weight of polyvinylidene fluoride of binding agent and an amount of N-N-methyl-2-2-pyrrolidone N-, just mix the anode mixture slurry thus.
And then, this anode mixture slurry is coated on the two sides of the above-mentioned collector body that obtains 65 and carries out drying, carry out pressure processing afterwards, thereby the thickness of producing gross thickness 126 μ m, positive electrode active material layer single face is the positive pole of the present invention of 58 μ m.This positive pole slitting cut be processed into predetermined width, thereby produce positive plate.
Shown in Figure 13 (a), banded collector body 65 has the roughly rounded protuberance 11 that the tightst filling is arranged, and has sufficient durability for the tensile stress that is applied on the long side direction Y.Therefore, in the formation operation of positive electrode active material layer and slitting are cut manufacturing procedure etc., can prevent local distortion and deflection, thereby suppress coming off of positive electrode active material layer.Therefore, can obtain not having distortion and deflection and be formed uniformly the positive plate of positive electrode active material layer.
Embodiment 2
(1) making of collector body
It is 10 μ m that installation is formed with a plurality of degree of depth, roughly assume diamond in shape and section configuration is that the ceramic roller of recess of coniform shape (bottom surface diameter 15 μ m, opening diameter 20 μ m) is as the roller 15 of collector body manufacturing installation 20 shown in Figure 5.Making as collector body is that the Copper Foil of 12 μ m vises the 21a of portion adding to depress by the crimping of collector body manufacturing installation 21 with the thickness of material web 23, carrying out compression process and non-compression process, thereby produces collector body shown in Figure 14 66.Figure 14 has schematically illustrated the formation as the collector body 66 of one of embodiments of the present invention.Figure 14 (a) is the vertical view of collector body 66.Figure 14 (b) is the longitudinal section of collector body 66.That is to say, be the cutaway view of thickness direction.
Resulting collector body 66 comprises that the base material portion 10 that is made of copper and the height that forms regularly on the two sides of the thickness direction of base material portion 10 are 6 μ m and the protuberance 67 that roughly assumes diamond in shape, and is total thickness t 2It is the collector body of the band shape of 18 μ m.On Width (short side direction) X, be formed with protuberance 67 with spacing P 5Be arranged in the capable unit 69 of row.On long side direction Y, row unit 69 is with spacing P 6Be arranged in parallel.Moreover, be expert at unit 69 and the capable unit 69 that is adjacent in, each protuberance 67 is configured to be offset 0.5P on Width X 5Distance.The Pareto diagram of such protuberance 67 is owing to being that the tightst filling is arranged, so collector body 66 has sufficient durability for the tensile stress that is applied on the long side direction Y.Therefore, when collector body 66 is processed as positive pole, when the positive pole that will obtain is processed as the size that is suitable for battery sizes etc., can prevent the local deformation and the deflection that on collector body 66, produce.
For the collector body 66 that obtains, measure surface with surface roughometer as Copper Foil, the plane 67a of the top ends of result on the bearing of trend of protuberance 67 be with processing before the roughly equal surface roughness of Copper Foil.In addition, (SEM) observes protuberance 67 with scanning electron microscope, and the result has seen and processed the same tiny scratch of observed scratch on the preceding Copper Foil.On the other hand, compare before with processing protuberance 67, the surface roughness of concave surface 68 reduces, and the surface roughness of this surface roughness and ceramic roller is roughly equal.
Moreover, for collector body 66, having carried out resolving based on the crystal orientation of Electron Back-Scattered Diffraction style (EBSP) method, the result compares before observing protuberance 67 and concave surface 68 and processing, and crystal grain attenuates little.In addition, measure the result of the hot strength of collector body 66,, can infer that hot strength is improved under the effect based on the work hardening of compression process although, do not see the reduction of hot strength in the segment thickness attenuation of concave surface 68.
According to above analysis result, can think if on Copper Foil, implement above-mentioned processing, then keeping the not state of compression process with the opposed noncontact face of the recess of ceramic roller, and contact-making surface in addition is implemented compression process, shown in Figure 14 (b), this can obtain having the not collector body 66 of the protuberance 67 of the top ends plane 67a of compression process being compressed to have formed in the base material portion 10 of processing.
(2) making of negative pole
Using purity as target is 99.9999% silicon, employing has the evaporation coating device of electron beam heating arrangements, to being formed with highly is that the two sides of collector body 66 of protuberance 67 of 6 μ m is that 99.7% oxygen carries out evaporation while importing purity, and growth consists of SiO on protuberance 67 0.5Columnar-shaped particle, forming thickness is the negative electrode active material layer of 20 μ m, thereby produces banded negative pole of the present invention.This negative pole slitting cut be processed into predetermined width, just produce negative plate.
Shown in Figure 14 (a), banded collector body 66 is owing to having the protuberance that roughly assumes diamond in shape 67 that the tightst filling is arranged, so to the long side direction Y of collector body 66 evaporation alloy system negative electrode active material the time, can make it efficiently attached on the protuberance 67.In addition, collector body 66 has sufficient durability for the tensile stress that is applied on the long side direction Y.Therefore, in cut manufacturing procedure etc. as the formation operation of the columnar-shaped particle of negative electrode active material layer and slitting, can prevent local distortion and deflection, thereby suppress coming off of negative electrode active material layer.Therefore, can obtain the negative plate that do not have distortion and deflection, be formed uniformly negative electrode active material layer.
Embodiment 3
Adopt following method to make rechargeable nonaqueous electrolytic battery 40 shown in Figure 11.
(1) making of collector body
The concave depth that is formed at ceramic roller surfaces is changed to 10 μ m, and used thickness be the Copper Foil of 18 μ m as collector body with material web 23, in addition, produce collector body 65 similarly to Example 1.Resulting collector body 65 comprises that base material portion 10 that is made of copper and the height that forms regularly on the two sides of base material portion 10 thickness directions are 8 μ m and roughly rounded protuberance 11, and is total thickness t 2It is the collector body of the band shape of 26 μ m.
The Pareto diagram of the protuberance 11 of collector body 65 is arranged for the tightst filling.Therefore, this collector body 65 has sufficient durability for the tensile stress that is applied on the long side direction Y.Therefore, when collector body 65 is processed as electrode, when the electrode that obtains being processed into the size that is suitable for battery sizes etc., can prevent to produce local distortion and deflection.
For collector body 65, measure surface with surface roughometer as Copper Foil, the plane 11a of the top ends of result on the bearing of trend of protuberance 11 be with processing before the roughly equal surface roughness of Copper Foil.In addition, (SEM) observes protuberance 11 with scanning electron microscope, and the result has seen and processed the same tiny scratch of observed scratch on the preceding Copper Foil.On the other hand, compare before with processing protuberance 11, the surface roughness of concave surface 12 reduces, and the surface roughness of this surface roughness and ceramic roller is roughly equal.
Moreover, for collector body 65, having carried out resolving based on the crystal orientation of Electron Back-Scattered Diffraction style (EBSP) method, the result compares before observing protuberance 11 and concave surface 12 and processing, and crystal grain attenuates little.In addition, measure the result of the hot strength of collector body 65,, can infer that hot strength is improved under the effect based on the work hardening of compression process although, do not see the reduction of hot strength in the segment thickness attenuation of concave surface 12.
According to above analysis result, can think if on Copper Foil, implement above-mentioned processing, then keeping the not state of compression process with the opposed noncontact face of the recess of ceramic roller, and contact-making surface in addition is implemented compression process, shown in Figure 13 (b), this can obtain having the not collector body 65 of the protuberance 11 of the top ends plane 11a of compression process being compressed to have formed in the base material portion 10 of processing.
(2) making of negative pole
Using purity as target is 99.9999% silicon, employing has the evaporation coating device of electron beam heating arrangements, to being formed with highly is that the two sides of collector body 65 of protuberance 11 of 8 μ m is that 99.7% oxygen carries out evaporation while importing purity, and growth consists of SiO on protuberance 11 0.5Columnar-shaped particle, forming thickness is the negative electrode active material layer of 25 μ m, thereby produces banded negative pole of the present invention.This negative pole slitting cut be processed into predetermined width, just produce negative plate 51.
Shown in Figure 13 (a), banded collector body 65 is owing to having the roughly rounded protuberance 11 that the tightst filling is arranged, so to the long side direction Y of collector body 65 evaporation alloy system negative electrode active material the time, can make it efficiently attached on the protuberance 11.In addition, collector body 65 has sufficient durability for the tensile stress that is applied on the long side direction Y.Therefore, in cut manufacturing procedure etc. as the formation operation of the columnar-shaped particle of negative electrode active material layer and slitting, can prevent local distortion and deflection, thereby suppress coming off of negative electrode active material layer.Therefore, can obtain not having distortion and deflection, be formed uniformly the negative plate 51 of negative electrode active material layer.
(3) Zheng Ji making
Similarly to Example 1, producing gross thickness is that the thickness of 126 μ m, positive electrode active material layer single face is the positive pole of the present invention of 58 μ m.This positive pole slitting cut be processed into predetermined width, just produce positive plate 50.
(4) allotment of nonaqueous electrolyte
Nonaqueous electrolytic solution uses in the mixed solvent that contains ethylene carbonate (EC) and methyl ethyl carbonate (EMC) with volume ratio at 1: 1, with the concentration dissolving LiPF of 1.0mol/L 6And the solution that obtains.
Superimposed and the above-mentioned positive plate that obtains 50 of reeling, barrier film 52 (polyethylene microporous film, thickness are 20 μ m, and Asahi Chemical Industry's (strain) produces), negative plate 51 and barrier film 52 are to make electrode group 41.An end that on the collector body exposed division of positive plate 50, connects positive wire 42.An end that on the collector body exposed division of negative plate 51, connects negative wire 43.Electrode group 41 and insulation board 44 are accommodated in the inside of the battery container 47 of round-ended cylinder shape, the other end of negative wire 43 is connected the bottom of battery container 47, then positive wire 42 is connected on the hush panel 45, in battery container 47, injects nonaqueous electrolyte 4.2ml.Then, will be installed on the peristome of the hush panel 45 insertion battery containers 47 of packing ring 46, and the inside bending of the peristome of battery container 47 is carried out ca(u)lk and sealed, just produce rechargeable nonaqueous electrolytic battery 40 of the present invention thus at periphery.
In above-mentioned non-aqueous secondary battery 40, complete and be wound into after the spiral helicine electrode group 41, this electrode group 41 of disintegrating is also observed, and the result does not all find unfavorable conditions such as coming off of battery lead plate fracture and electrode active material mixture layer on positive plate 50 and negative plate 51.Moreover, this non-aqueous secondary battery 40 is carried out 300 times charge and discharge cycles, but do not observed the circulation deterioration.In addition, after 300 circulations, disintegration non-aqueous secondary battery 40 and electrode group 41, result are not found lithium separating out and the unfavorable condition such as come off of active material layer on negative plate 51.
Can think thus: by the film of active material layer being formed column at the upper surface of the protuberance of compression process not, can obtain following effect: the change in volume that the contraction of the film of the active material layer the when expansion of the active material layer film when making because of the embedding lithium and removal lithium embedded causes is relaxed, and can keep good battery behavior thus.
Shown in embodiment 1～3, in electrode of the present invention, because the plane on the protuberance top of collector body is in the not state of compression process, so can be not residual by implementing the caused processing strain of processing, the surface accuracy on protuberance plane is good, thereby makes the formation of homogeneous film become possibility.In addition, can also think: by implementing not compression process, surface roughness can not reduce yet, and is still keeping the surface roughness at initial stage, so can improve and the adhesive force that forms the active material layer of film.
On this angle, can think that making collector body in advance is very effective with the surperficial chap of material web in order further to improve the adhesive force of protuberance plane and active material layer.
In addition, shown in embodiment 3, the active material layer of non-aqueous secondary battery of the present invention is preferred mainly to form column on the plane of the not compression process of protuberance.The change in volume that the contraction of the active material layer in the time of thus, can relaxing the expansion of and active material layer when embedding lithium together with discharging and recharging of non-aqueous secondary battery and removal lithium embedded causes.Consequently, can not take place because of discharging and recharging unfavorable condition such as coming off of the battery lead plate fracture that causes and active material layer, thereby can obtain high power capacity and the high non-aqueous secondary battery of reliability.
Embodiment 4
(1) making of negative electrode collector
Roller shown in Figure 4 15 and the iron roller that has an even surface are loaded in the collector body manufacturing installation 26 shown in Figure 8.Roller 15 is made of central part and skin section, and wherein central part is an iron, and skin section is a chromium oxide, and recess 16 with the arranged in patterns of rule from the teeth outwards.The degree of depth of recess 16 is 9.5 μ m, and in the section of recess 16, the line of the side of expression recess 16 approximately tilts 20 ° with respect to the direction with roller 15 Surface Vertical.That is, the section of recess 16 is coniform shape, and its bottom 16a from recess 16 approaches opening 16b more, and cross section diameter just increases.In addition, the diameter of the opening 16b of recess 16 is 18 μ m.
Making as collector body is that the rolled copper foil (Japanese foliation (strain) production) of 18 μ m is to vise portion by the crimping of collector body manufacturing installation 26 under the pressure of 1 ton/cm at line pressure with the thickness of material web 23, carrying out compression process and non-compression process, thereby produce the of the present invention collector body same with collector body shown in Figure 8 25.This collector body has following feature:
The thickness of base material portion: 12 μ m
The shape of protuberance: roughly be truncated cone shape
The section configuration of protuberance: the coniform shape that cross section diameter reduces to the protuberance top
The height L:7 μ m of protuberance
Protuberance is at the diameter D of 0.3L height 0.3: 9.5 μ m
Protuberance is at the diameter D of 0.5L height 0.5: 6.0 μ m
Protuberance is at the diameter D of 0.8L height 0.8: 4.0 μ m
D 0.5/D 0.3：0.63
D 0.8/D 0.5：0.67
(2) formation of negative electrode active material layer
On the surface of the above-mentioned collector body that obtains, form active material layer by evaporation, thereby produce negative pole of the present invention.
Evaporation uses evaporation coating device 70 ((strain) ULVAC production) shown in Figure 15.Figure 15 is the longitudinal section that schematically illustrates the formation of evaporation coating device 70.Evaporation coating device 70 comprises that chamber 71, fixed station 72, gas emits nozzle 73, gas pipeline 74 and target 75.Fixed station 72, nozzle 73, gas pipeline 74 and target 75 have been taken in chamber 71 portion space within it.In addition, not shown rotary pump is connected with chamber 71 with diffusion pump, can adjust the vacuum degree of its inner space.Fixed station 72 is subjected to the support of not shown support component in freely mode of rotation, and is included on the surface of thickness direction the fixedly fixed mechanism of collector body 76.By making fixed station 72 rotations, adjust the surperficial 72a and the horizontal plane 80 angulation α of fixed station 72, and then adjust the direction of growth of the active material layer on collector body 76 surfaces.
Nozzle 73 is built up in the below of the vertical direction of fixed station 72, to emit the unstrpped gas of active material.As unstrpped gas, for example can list oxygen, nitrogen etc.In addition, under the situation that forms the active material layer that only is made of Si or Sn, control nozzle 73 is not so that can emit unstrpped gas.Gas pipeline 74 is connected with the not shown raw material gas cylinder that is built in evaporation coating device 70 outsides, to nozzle 73 base feed gases.Target 75 is set in vertical direction: it is mutually opposed with fixed station 72 by nozzle 73 to be situated between.In addition, the not shown platform and be used to of target 75 with the mounting of being used for active material or its raw material (for example, Si, Sn etc.) heats active material or its raw material and makes the electron beam heating arrangements of its gasification.Target 75 makes the steam of active material emit to the top of vertical direction.As required with after unstrpped gas is mixed, arrived and be attached to the surface of collector body 76 by the active material steam of being emitted.Thus, just form active material layer.
In evaporation coating device shown in Figure 15 70, it is 70 ° thereby fixed station 72 inclinations make surperficial 72a and horizontal plane 80 angulation α.Collector body 76 is made the size that the above-mentioned collector body that obtains cuts into 40mm * 40mm.Collector body 76 is fixed on the fixed station 72 towards the mode below the vertical direction with the surface that is formed with protuberance.In addition, target 75 use purity are 99.9999% elementary silicon (production of (strain) high-purity chemical research institute).Carrying out exhaust makes the vacuum degree in the chamber 71 reach 5 * 10 -5Torr.The accelerating voltage that is radiated at the electron beam on the target 75 of elementary silicon is set at-8kV, and (emission) is set at 500mA with emission current.In addition, emitting purity from nozzle 73 with the flow of 30sccm is 99.7% oxygen (Japanese oxygen (strain) production).At this moment the vacuum degree in the chamber 71 probably is 2 * 10 -4Torr.Evaporation carried out 30 minutes.
The steam of the elementary silicon that will emit from target 75 is deposited on the collector body 76 that is fixed in fixed station 72 with the oxygen of emitting from nozzle 73.Thus, just form and contain the negative electrode active material layer of the columnar-shaped particle that constitutes by Si oxide, thereby obtain negative pole of the present invention.According to firing method and ICP luminescence analysis oxygen amount that negative electrode active material contained and silicon amount in the columnar-shaped particle that generates have been carried out quantitatively, the result under any circumstance, the composition of negative electrode active material is SiO 0.5
Secondly, as shown in figure 10, constitute the columnar-shaped particle of negative electrode active material layer and direction angulation θ for research perpendicular to the collector body surface 1, observe with the section of scanning electron microscope anticathode.The section of negative pole is confirmed as: with parallel perpendicular to the direction on collector body surface, comprise the peak of the protuberance of collector body, and the section of protuberance reaches maximum.Figure 16 is the scanning electron microscope photo of the negative pole section of embodiment 4.As shown in Figure 17: columnar-shaped particle tilts with respect to the direction with the Surface Vertical of collector body, and appendix spreads all over the zone of side at the upper surface from the collector body protuberance.In addition, angle θ 1It is 27 °.This value averages the measured value of any 10 columnar-shaped particles and obtains.
The main rerum natura of the negative pole of embodiment 4 is as follows:
The composition of active material: SiO 0.5
θ 1：27°
The thickness T of active material layer: 24 μ m
Embodiment 5
(1) making of negative electrode collector
The degree of depth of recess 16 is changed to 11 μ m by 9.5 μ m, in the section of recess 16, with the line of the side of expression recess 16 with respect to changing to about 10 ° by about 20 ° with the angle at the angle that direction becomes of roller 15 Surface Vertical, and the diameter of the opening 16b of recess 16 changed to about 14 μ m by 18 μ m, in addition, produce collector body of the present invention similarly to Example 4.This collector body has following feature:
The thickness of base material portion: 12 μ m
The shape of protuberance: roughly be truncated cone shape
The section configuration of protuberance: the coniform shape that cross section diameter reduces to the protuberance top
The height L:9 μ m of protuberance
Protuberance is at the diameter D of 0.3L height 0.3: 10 μ m
Protuberance is at the diameter D of 0.5L height 0.5: 9.0 μ m
Protuberance is at the diameter D of 0.8L height 0.8: 7.3 μ m
D 0.5/D 0.3：0.9
D 0.8/D 0.5：0.81
(2) formation of negative electrode active material layer
Except that using embodiment 5 resulting collector bodies, form negative electrode active material layer similarly to Example 4, thereby produce negative pole of the present invention.With scanning electron microscope the section of the negative pole that obtains is observed.Figure 17 is the scanning electron microscope photo of the negative pole section of embodiment 5.The principal character of the negative pole of embodiment 5 is as follows:
The composition of active material: SiO 0.5
θ 1：25°
The thickness T of active material layer: 25 μ m
Embodiment 6
(1) negative electrode collector is made
It at thickness (Japanese foliation (strain) production) coating negative type photoresist on the rolled copper foil of 12 μ m.Use has the minus mask of the square chopping point pattern of 10 μ m with the arranged spaced of 20 μ m, and the resist film on the Copper Foil is exposed and develops., in the hole of the resist film that form, by means of electrolysis copper particle separated out, remove resist then thereafter.Consequently, can obtain having the collector body of the present invention of the protuberance that roughly is quadrangular pyramid platform shape.This collector body has following feature:
The thickness of base material portion: 12 μ m
The section configuration of protuberance: the coniform shape that cross section diameter reduces to the protuberance top
The height L:8 μ m of protuberance
Protuberance is at the diameter D of 0.3L height 0.3: 10 μ m
Protuberance is at the diameter D of 0.5L height 0.5: 9.8 μ m
Protuberance is at the diameter D of 0.8L height 0.8: 9.3 μ m
D 0.5/D 0.3：0.98
D 0.8/D 0.5：0.95
(2) formation of negative electrode active material layer
Use embodiment 6 resulting collector bodies, and fixed station 72 is set at 60 ° with horizontal plane 80 angulation α, in addition, form negative electrode active material layer similarly to Example 4, thereby produce negative pole of the present invention.With scanning electron microscope the section of the negative pole that obtains is observed.Figure 18 is the scanning electron microscope photo of the negative pole section of embodiment 6.The principal character of the negative pole of embodiment 6 is as follows:
The composition of active material: SiO 0.5
θ 1：27°
The thickness T of active material layer: 25 μ m
Embodiment 7
(1) making of negative electrode collector
The degree of depth of recess 16 is changed to 10 μ m by 9.5 μ m, and in the section of recess 16, with the line of the side of expression recess 16 with respect to changing to about 10 ° by about 20 ° with the angle at the angle that direction becomes of roller 15 Surface Vertical, in addition, produce collector body of the present invention similarly to Example 4.This collector body has following feature:
The thickness of base material portion: 12 μ m
The shape of protuberance: roughly be truncated cone shape
The section configuration of protuberance: the coniform shape that cross section diameter reduces to the protuberance top
The height L:9 μ m of protuberance
Protuberance is at the diameter D of 0.3L height 0.3: 13 μ m
Protuberance is at the diameter D of 0.5L height 0.5: 10 μ m
Protuberance is at the diameter D of 0.8L height 0.8: 8.5 μ m
D 0.5/D 0.3：0.77
D 0.8/D 0.5：0.85
(2) formation of negative electrode active material layer
The surperficial 72a and the angle α that horizontal plane 80 is become of control fixed station 72 alternately change it between 60 ° and 120 °, in addition, form negative electrode active material layer similarly to Example 4, thereby produce negative pole of the present invention.To be that 6 layers small column piece is stacked be the columnar-shaped particle of Z word shape to the columnar-shaped particle that is contained in this negative electrode active material layer.With scanning electron microscope the section of this negative pole is observed.Figure 19 is the scanning electron microscope photo of the negative pole section of embodiment 7.The principal character of the negative pole of embodiment 7 is as follows:
The composition of active material: SiO 0.4
Columnar-shaped particle and the angle θ that direction became: 0 ° perpendicular to the collector body surface
The thickness T of active material layer: 24 μ m
(comparative example 1)
(1) making of negative electrode collector
It at thickness (Japanese foliation (strain) production) coating positive light anti-etching agent on the rolled copper foil of 12 μ m.Use has the eurymeric mask of the square pattern of 15 μ m with the arranged spaced of 30 μ m, and the resist film on the Copper Foil is exposed and develops., in the hole of the resist film that form, by means of electrolysis copper particle separated out, remove resist then thereafter.Consequently, can obtain having the collector body of the protuberance that roughly is the platform of falling quadrangular pyramid shape.
The rerum natura of collector body is as follows.
The thickness of base material portion: 18 μ m
The height L:7 μ m of protuberance
Protuberance is at the diameter D of 0.3L height 0.3: 11.5 μ m
Protuberance is at the diameter D of 0.5L height 0.5: 12.0 μ m
Protuberance is at the diameter D of 0.8L height 0.8: 13.5 μ m
D 0.5/D 0.3：1.04
D 0.8/D 0.5：1.13
(2) formation of negative electrode active material layer
Use comparative example 1 resulting collector body, and fixed station 72 is set at 60 ° with horizontal plane 80 angulation α, in addition, form negative electrode active material layer similarly to Example 4, thereby produce negative pole.With scanning electron microscope the section of the negative pole that obtains is observed.Figure 20 is the scanning electron microscope photo of the negative pole section of comparative example 1.The principal character of the negative pole of comparative example 1 is as follows:
The composition of active material: SiO 0.5
Columnar-shaped particle and the angle θ that direction became: 35 ° perpendicular to the collector body surface
The thickness T of active material layer: 23 μ m
Use embodiment 4～7 and comparative example 1 resulting negative pole, adopt following method to produce as shown in figure 12 cascade type lithium secondary battery.
(1) Zheng Ji making
The cobalt acid lithium (LiCoO that will be about 10 μ m as the average grain diameter of positive active material 2) powder 10g, as the acetylene black 0.3g of conductive agent, mix fully as the Kynoar powder 0.8g of binding agent and an amount of N-N-methyl-2-2-pyrrolidone N-(NMP), thereby mix the anode mixture slurry.
Being coated on the anode mixture slurry that obtains by thickness is on the single face of the positive electrode collector 56a that constitutes of the aluminium foil of 20 μ m, rolls after the drying, thereby form positive electrode active material layer 56b.With anodal 56 be cut into predetermined shape thereafter.In anodal 56, appendix has the size of thickness and the 30mm * 30mm of 70 μ m at the positive electrode active material layer 56b of aluminium foil single face.The back side at the positive electrode collector 56a that does not have positive electrode active material layer 56b is connecting positive wire 60.
(2) making of battery
Make the positive pole of separating by barrier film 58 (polyethylene microporous film, thickness are 20 μ m, Asahi Chemical Industry's (strain) produce) 56 mutually opposed with negative pole 57 (negative pole of embodiment 4～7 and comparative example 1) and constitute the electrode group.The back side at the negative electrode collector 57a that does not have negative electrode active material layer 57b is connecting negative wire 61.
Secondly, the electrode group is inserted in the external shell 59 that constitutes by the folded thin slice of aluminium lamination.In housing, inject nonaqueous electrolytic solution then.Nonaqueous electrolytic solution uses in the mixed solvent that contains ethylene carbonate (EC) and methyl ethyl carbonate (EMC) with volume ratio at 1: 1, with the concentration dissolving LiPF of 1.0mol/L 6And the solution that obtains.Adopt vacuum impregnation technology, nonaqueous electrolytic solution be impregnated in positive pole 56, negative pole 57 and the barrier film 58.
, making positive wire 60 and negative wire 61 to the state of outside derivation under thereafter, and carry out vacuum decompression, and meanwhile weld sealing resin 62 in the open end configuration of external shell 59, thus produce the battery of embodiment 4～7 and comparative example 1.
(test example 1)
The battery of embodiment 4～7 and comparative example 1 is accommodated in respectively in 20 ℃ the thermostatic chamber, carries out cyclic test in the mode of constant current constant voltage.
At first, reach 4.2V until cell voltage, reach after the 4.2V, reach 0.05C until current value with the constant voltage charging with the constant current charge of 1C speed (so-called 1C is meant with the current value that can use the entire cell capacity in 1 hour).
After charging finishes, stop 20 minutes after, discharge with the constant current of 1C speed, reach 2.5V until cell voltage.Thereafter, further the constant current with 0.2C speed discharges, and reaches 2.5V until cell voltage.Discharge stops 20 minutes after finishing.
Above-mentioned discharge and recharge 20 times repeatedly circulate.With the whole discharge capacity of the 20th circulation with respect to the ratio of whole discharge capacity at circulation initial stage as the capacity sustainment rate, and obtain with percentage.Result such as table 1 expression.In addition, the battery after the resolution test confirms to have or not peeling off of collector body protuberance.
Table 1
? D 0.5/D 0.3 Capacity sustainment rate (%) Have or not and peel off θ 1?(°)
Embodiment 4 0.63 96 Do not have 27
Embodiment 5 0.90 97 Do not have 25
Embodiment 6 0.98 90 Do not have 27
Embodiment 7 0.77 97 Do not have 0
Comparative example 1 1.04 50 Have 35
As shown in table 1, obviously the battery of embodiment 4～7 is compared with the battery of comparative example 1, and the capacity sustainment rate after 20 circulations is all bigger, and cycle characteristics is improved significantly.In addition, after 20 circulations, divide electrolytic cell and anticathode is observed, the result just in comparative example 1, peel off from collector body by active material.Observe in detail the result of peeling off the position, obviously on the interface of the base material portion of collector body and protuberance, taken place to peel off.On the other hand, in the negative pole of embodiment 4～7, do not observe peeling off at the interface of base material portion and protuberance.This can think: in the negative pole of the battery of comparative example 1, because protuberance has the platform of falling quadrangular pyramid shape, thus can not disperse or relax stress fully in the generation of the interface of protuberance and base material portion, thus the capacity sustainment rate reduces significantly.
Rechargeable nonaqueous electrolytic battery of the present invention for example can preferably utilize the non-aqueous electrolyte lithium secondary battery as variety of way.Especially, the preferred use as the lithium secondary battery that requires high power capacity and good cycle characteristics.Can be suitable for not special qualification of shape of lithium secondary battery of the present invention, for example also can be Any shape such as Coin shape, button type, sheet type, cylinder type, platypelloid type, square.The mode of the electrode group that is made of anodal, negative pole and barrier film both can be convoluted, also can be cascade type.The size of battery both can be used for miniature portable equipment etc. small-sized, also can be used for electric automobile etc. large-scale.Lithium secondary battery of the present invention for example can be applied to the power supply of portable information terminal, mancarried electronic aid, domestic small electric power storing device, automatic two-wheeled cycle, electric automobile, hybrid-electric car etc., does not limit but its purposes is special.

Claims (17)

1. electrode, it comprises:
Collector body, comprise base material portion and form from described base material portion surface a plurality of protuberances that extend to the outside of described base material portion, wherein, the section of the described protuberance of described collector body thickness direction towards the direction that described protuberance extends, is the coniform shape of the narrowed width of the direction that is parallel to described base material portion surface from described base material portion surface; And
Active material layer, it comprises and contains active material and form the columnar-shaped particle that extends to the outside of described collector body from the described protuberance surface of described collector body.
2. electrode according to claim 1, wherein, protuberance has height L, and at the diameter D of the protuberance of 0.3L height 0.3Greater than diameter D at 0.8L protuberance highly 0.8
3. electrode according to claim 1, wherein, protuberance has height L, at the diameter D of 0.5L protuberance highly 0.5With diameter D at 0.3L protuberance highly 0.3Ratio D 0.5/ D 0.3Be below 0.98.
4. electrode according to claim 1, wherein, protuberance has height L, at the diameter D of 0.8L protuberance highly 0.8With diameter D at 0.5L protuberance highly 0.5Ratio D 0.8/ D 0.5Be more than 0.4.
5. electrode according to claim 1, wherein, in the section of collector body thickness direction, at least one among the line angulation θ on the surface of the line of the side of expression protuberance and expression base material portion is greater than 90 ° but less than 160 °.
6. wherein, there is not the interface in electrode according to claim 1 between base material portion and protuberance, and the crystalline portion that contains from base material portion to the protuberance continued presence at least and have identical substantially crystalline state.
7. electrode according to claim 1, wherein, protuberance forms by compression process not.
8. electrode according to claim 1, wherein, on the bearing of trend of protuberance, the head portion of protuberance is the plane.
9. electrode according to claim 1, wherein, protuberance is shaped as circle, ellipse, polygonal, fan-shaped or crescent in orthographic drawing.
10. electrode according to claim 1, wherein, protuberance is arranged in staggered clathrate or chessboard trellis on base material portion surface.
11. electrode according to claim 1, wherein, columnar-shaped particle tilts with respect to the direction with the collector body Surface Vertical.
12. electrode according to claim 1, wherein, columnar-shaped particle is the duplexer that contains a plurality of column pieces of active material.
13. electrode according to claim 1, wherein, active material is the compound that is selected from least a kind alloy system negative electrode active material among silicon, tin, germanium and the aluminium and/or contains the alloy system negative electrode active material.
14. electrode according to claim 13, wherein, the compound that contains the alloy system negative electrode active material is at least a kind that is selected among at least a kind alloy, oxide and the sulfide that contains the alloy system negative electrode active material.
15. electrode according to claim 1, wherein, being shaped as of columnar-shaped particle is cylindric, circular cone shape, rounding frustum, prism-shaped, prismatic platform shape or chamfered edge pylon shape.
16. electrode according to claim 14, wherein, the compound that contains the alloy system negative electrode active material is at least a kind the oxide that contains the alloy system negative electrode active material, and described oxide is SiO xOr SnO x, 0＜x＜2 wherein.
17. a rechargeable nonaqueous electrolytic battery, it comprises the nonaqueous electrolyte to electrode and lithium-ion-conducting of the described electrode of claim 1, this electrode.
CN2007800323307A 2006-08-29 2007-08-28 Current collector, electrode, and non-aqueous electrolyte secondary battery Expired - Fee Related CN101512799B (en)

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